CN110590736A - Synthesis method of 2-thiophene glyoxylic acid - Google Patents
Synthesis method of 2-thiophene glyoxylic acid Download PDFInfo
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- GIWRVUADKUVEGU-UHFFFAOYSA-N 2-oxo-2-thiophen-2-ylacetic acid Chemical compound OC(=O)C(=O)C1=CC=CS1 GIWRVUADKUVEGU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000012452 mother liquor Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 13
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000005457 ice water Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- SMJRBWINMFUUDS-UHFFFAOYSA-N 2-thienylacetic acid Chemical compound OC(=O)CC1=CC=CS1 SMJRBWINMFUUDS-UHFFFAOYSA-N 0.000 claims 7
- 238000000605 extraction Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- DXOKISNPYGAEFJ-UHFFFAOYSA-N oxaldehydic acid;thiophene Chemical compound C=1C=CSC=1.OC(=O)C=O DXOKISNPYGAEFJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- AJYXPNIENRLELY-UHFFFAOYSA-N 2-thiophen-2-ylacetyl chloride Chemical compound ClC(=O)CC1=CC=CS1 AJYXPNIENRLELY-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机合成领域，具体涉及一种2‑噻吩乙醛酸的合成方法。以亚硝酰硫酸为氧化剂，在硫酸溶液中与2‑乙酰噻吩反应，经精制得到2‑噻吩乙醛酸。精制为将反应液倒入冰水中，析晶过滤，将得到的固体加碱溶解，调pH至2～5，再加入溶剂萃取除杂，最后再继续加酸调pH至0.8～1。本发明是一种由2‑乙酰噻吩制备2‑噻吩乙醛酸的新方法，该方法没有盐产生，溶剂没有挥发性，减少了挥发性气体的设备腐蚀，操作条件有改善，制备得到的2‑噻吩乙醛酸纯度在98.5％以上，收率在81％以上；本发明母液通过简单处理可以套用，减少了环境污染，更加环保。The invention belongs to the field of organic synthesis, in particular to a method for synthesizing 2-thiophene glyoxylic acid. Using nitrosyl sulfuric acid as an oxidizing agent, it reacts with 2-acetylthiophene in sulfuric acid solution to obtain 2-thiophene glyoxylic acid after purification. The refining method is to pour the reaction liquid into ice water, crystallize and filter, dissolve the obtained solid with alkali, adjust the pH to 2-5, then add solvent to extract and remove impurities, and finally add acid to adjust the pH to 0.8-1. The present invention is a new method for preparing 2-thiophene glyoxylic acid from 2-acetylthiophene. In the method, no salt is generated, the solvent has no volatility, equipment corrosion caused by volatile gases is reduced, operating conditions are improved, and the prepared 2 The purity of thiophene glyoxylic acid is above 98.5%, and the yield is above 81%. The mother liquor of the present invention can be applied mechanically through simple treatment, which reduces environmental pollution and is more environmentally friendly.
Description
技术领域technical field
本发明属于有机合成领域，具体涉及一种2-噻吩乙醛酸的合成方法。The invention belongs to the field of organic synthesis, in particular to a method for synthesizing 2-thiopheneglyoxylic acid.
背景技术Background technique
2-噻吩乙醛酸是一种2-噻吩乙酰氯的中间体，通常由2-乙酰噻吩和亚硝酸钠/盐酸反应得到。该方法在反应过程中会产生氯化钠为固废，同时盐酸由于其挥发性对设备有强烈腐蚀，操作条件恶劣，而且母液为高盐强酸废液，污染严重。2-thiophene glyoxylic acid is an intermediate of 2-thiophene acetyl chloride, usually obtained by reacting 2-acetylthiophene with sodium nitrite/hydrochloric acid. In this method, sodium chloride will be produced as solid waste in the reaction process, and hydrochloric acid will strongly corrode equipment due to its volatility, and the operating conditions are harsh, and the mother liquor is high-salt and strong acid waste liquid, causing serious pollution.
发明内容Contents of the invention
针对现有技术的不足，本发明的目的是提供一种2-噻吩乙醛酸的合成方法，该方法没有盐产生，溶剂没有挥发性，减少了挥发性气体的设备腐蚀，操作条件有改善；母液通过简单处理可以套用，减少了环境污染，更加环保。For the deficiencies in the prior art, the purpose of the present invention is to provide a kind of synthetic method of 2-thiophene glyoxylic acid, this method does not produce salt, and solvent has no volatility, reduces the equipment corrosion of volatile gas, and operating condition is improved; The mother liquor can be applied mechanically through simple treatment, which reduces environmental pollution and is more environmentally friendly.
本发明所述的2-噻吩乙醛酸的合成方法，以亚硝酰硫酸为氧化剂，在硫酸溶液中与2-乙酰噻吩反应，经精制得到2-噻吩乙醛酸。The synthesis method of 2-thiopheneglyoxylic acid of the present invention uses nitrosyl sulfuric acid as an oxidant, reacts with 2-acetylthiophene in a sulfuric acid solution, and obtains 2-thiopheneglyoxylic acid through refining.
反应方程式如下：The reaction equation is as follows:
其中：in:
亚硝酰硫酸为市售的浓度为40％的亚硝酰硫酸的硫酸溶液，本发明在硫酸溶液条件下反应，不需要引入其他溶剂，同时本发明硫酸也可以进行回收。Nitrosyl sulfuric acid is a commercially available sulfuric acid solution of nitrosyl sulfuric acid with a concentration of 40%. The present invention reacts under the condition of sulfuric acid solution without introducing other solvents. Simultaneously, the sulfuric acid of the present invention can also be recovered.
硫酸溶液的浓度为20％～98％，优选50～80％。The concentration of the sulfuric acid solution is 20%-98%, preferably 50-80%.
硫酸溶液的用量为2-乙酰噻吩重量的0.5～50倍，如果硫酸的用量太少，体系太稠反应效果不好，如果硫酸的用量太多，造成浪费，且反应效果不好。The amount of sulfuric acid solution is 0.5 to 50 times the weight of 2-acetylthiophene. If the amount of sulfuric acid is too small, the system is too thick and the reaction effect is not good. If the amount of sulfuric acid is too much, it will cause waste and the reaction effect is not good.
亚硝酰硫酸用量为2-乙酰噻吩重量的2-10倍，此用量反应效果最好。The dosage of nitrosyl sulfuric acid is 2-10 times of the weight of 2-acetylthiophene, and the reaction effect of this dosage is the best.
反应温度为-10～40℃，优选0～10℃。The reaction temperature is -10 to 40°C, preferably 0 to 10°C.
精制为将反应液倒入冰水中，析晶过滤，将得到的固体加碱溶解，调pH至2～5，再加入溶剂萃取除杂，最后再继续加酸调pH至0.8～1。第一次加碱调pH可以除去2-噻吩甲酸杂质，第二次再加酸调回0.8-1得到产品。The refining method is to pour the reaction liquid into ice water, crystallize and filter, dissolve the obtained solid with alkali, adjust the pH to 2-5, then add solvent to extract and remove impurities, and finally add acid to adjust the pH to 0.8-1. Adding alkali for the first time to adjust the pH can remove the impurity of 2-thiophenecarboxylic acid, and adding acid for the second time to adjust it back to 0.8-1 to obtain the product.
析晶过滤后得到的母液减压浓缩至硫酸浓度为65％-70％后套用于下一批。The mother liquor obtained after crystallization and filtration is concentrated under reduced pressure to a sulfuric acid concentration of 65%-70%, and then used in the next batch.
母液回收工艺为：向回收母液中加入2-乙酰噻吩，搅拌降温，将亚硝酰硫酸加至反应液中，控制内温-10～40℃，滴加完后继续保温搅拌反应，将反应液缓慢倒入冰水中，继续冷冻析晶，过滤，得到黄色固体，经精制得到2-噻吩乙醛酸。The mother liquor recovery process is: add 2-acetylthiophene to the recovered mother liquor, stir to cool down, add nitrosyl sulfuric acid to the reaction liquid, control the internal temperature -10 ~ 40 ° C, continue to keep warm and stir the reaction after the dropwise addition, and the reaction liquid Slowly pour it into ice water, continue to freeze and crystallize, and filter to obtain a yellow solid, which is purified to obtain 2-thiopheneglyoxylic acid.
溶剂为乙酸乙酯、甲酸乙酯、二氯甲烷、二氯乙烷、氯仿或甲苯。The solvent is ethyl acetate, ethyl formate, dichloromethane, dichloroethane, chloroform or toluene.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明是一种由2-乙酰噻吩制备2-噻吩乙醛酸的新方法，该方法没有盐产生，溶剂没有挥发性，减少了挥发性气体的设备腐蚀，操作条件有改善，制备得到的2-噻吩乙醛酸纯度在98.5％以上，收率在81％以上。(1) The present invention is a new method for preparing 2-thiophene glyoxylic acid from 2-acetylthiophene. The method does not produce salt, the solvent has no volatility, reduces equipment corrosion of volatile gases, and improves operating conditions. The purity of the obtained 2-thiopheneglyoxylic acid is above 98.5%, and the yield is above 81%.
(2)本发明母液通过简单处理可以套用，减少了环境污染，更加环保。(2) The mother liquor of the present invention can be applied mechanically through simple treatment, which reduces environmental pollution and is more environmentally friendly.
具体实施方式Detailed ways
下面结合实施例对本发明做进一步说明。The present invention will be further described below in conjunction with embodiment.
实施例1Example 1
向反应瓶中加入2-乙酰噻吩250g，浓度为70％的硫酸1500g，降温至10℃；控温15±3℃加入亚硝酰硫酸1000g加至反应液中，控制内温10±3℃，滴加完后继续保温搅拌反应0.6h后反应结束；将反应液缓慢倒入4.5L冰水中，析晶过滤，得到黄色固体；母液减压浓缩至硫酸浓度70％可继续套用至下一批反应。将得到的固体加碱水溶解，调pH到3后加乙酸乙酯萃取除杂，继续加酸调pH到1，过滤烘干得固体2-噻吩乙醛酸，纯度99.1％，收率81％。Add 250g of 2-acetylthiophene and 1,500g of sulfuric acid with a concentration of 70% to the reaction flask, and cool down to 10°C; add 1,000g of nitrosyl sulfuric acid to the reaction solution at a temperature control of 15±3°C, and control the internal temperature at 10±3°C. After the dropwise addition, continue to keep warm and stir for 0.6h to complete the reaction; slowly pour the reaction solution into 4.5L ice water, crystallize and filter to obtain a yellow solid; concentrate the mother liquor under reduced pressure to a sulfuric acid concentration of 70%, and continue to apply it to the next batch of reactions . Dissolve the obtained solid with alkaline water, adjust the pH to 3, add ethyl acetate to extract and remove impurities, continue to add acid to adjust the pH to 1, filter and dry to obtain solid 2-thiopheneglyoxylic acid, the purity is 99.1%, and the yield is 81%. .
实施例2Example 2
向5L四口瓶中加入2-乙酰噻吩250g，浓度为65％的硫酸1000g，搅拌降温至0℃；将亚硝酰硫酸1500g加至反应液中，控制内温2±3℃，滴加完后继续保温搅拌反应1h后，将反应液缓慢倒入4.5L冰水中，继续冷冻析晶3h，过滤，得到黄色固体；母液减压浓缩至含量65％后套用于下一批。将得到的固体加碱水溶解，调pH到3后加入二氯乙烷萃取除杂，继续加酸调pH到0.9，加二氯甲烷萃取，有机层蒸干得产品2-噻吩乙醛酸，纯度98.5％，收率83％。Add 250g of 2-acetylthiophene and 1000g of sulfuric acid with a concentration of 65% to a 5L four-necked bottle, stir and cool down to 0°C; add 1500g of nitrosyl sulfuric acid to the reaction solution, control the internal temperature at 2±3°C, and drop After continuing to insulate and stir the reaction for 1 hour, the reaction solution was slowly poured into 4.5 L of ice water, continued to freeze and crystallize for 3 hours, and filtered to obtain a yellow solid; the mother liquor was concentrated under reduced pressure to a content of 65% and used in the next batch. Dissolve the obtained solid with alkaline water, adjust the pH to 3, add dichloroethane to extract and remove impurities, continue to add acid to adjust the pH to 0.9, add dichloromethane to extract, and evaporate the organic layer to dryness to obtain the product 2-thiopheneglyoxylic acid. The purity is 98.5%, and the yield is 83%.
实施例3Example 3
向10L反应瓶中加入2-乙酰噻吩500g，浓度为60％的硫酸2000g，搅拌降温至0℃；将亚硝酰硫酸3000g加至反应液中，控制内温15±3℃，滴加完后继续保温搅拌反应1h后，将反应液缓慢倒入9L冰水中，继续冷冻析晶3h，过滤，得到黄色固体；母液减压浓缩至含量65％后套用于下一批。将得到的固体加碱水溶解，调pH到3后加入氯仿萃取除杂，继续加酸调pH到1，加二氯甲烷萃取，有机层蒸干得产品2-噻吩乙醛酸，纯度98.7％，收率84％。Add 500g of 2-acetylthiophene and 2000g of sulfuric acid with a concentration of 60% to a 10L reaction bottle, stir and cool down to 0°C; add 3000g of nitrosyl sulfuric acid to the reaction solution, control the internal temperature at 15±3°C, After continuing to insulate and stir for 1 hour, the reaction solution was slowly poured into 9 L of ice water, continued to freeze and crystallize for 3 hours, and filtered to obtain a yellow solid; the mother liquor was concentrated under reduced pressure to a content of 65% and used in the next batch. Dissolve the obtained solid with alkaline water, adjust the pH to 3, add chloroform to extract and remove impurities, continue to add acid to adjust the pH to 1, add dichloromethane to extract, and evaporate the organic layer to dryness to obtain the product 2-thiophene glyoxylic acid with a purity of 98.7% , yield 84%.
母液回收：Mother liquor recovery:
向硫酸含量65％的实施例1得到的回收母液3000g中加入2-乙酰噻吩500g，搅拌降温至0℃将亚硝酰硫酸3000g加至反应液中，控制内温-2±3℃，滴加完后继续保温搅拌反应1h后，将反应液缓慢倒入10L冰水中，继续冷冻析晶3h，过滤，得到黄色固体；母液减压浓缩至含量65％后套用于下一批。将得到的固体加碱水溶解，调pH到3后加入氯仿萃取除杂，继续加酸调pH到1，加二氯甲烷萃取，有机层蒸干得产品2-噻吩乙醛酸，纯度98.2％，收率88％。Add 500 g of 2-acetylthiophene to 3000 g of the recovered mother liquor obtained in Example 1 with a sulfuric acid content of 65%, stir and cool down to 0 °C, add 3000 g of nitrosyl sulfuric acid to the reaction solution, control the internal temperature to -2±3 °C, and add After the reaction was continued for 1 hour with insulation and stirring, the reaction solution was slowly poured into 10 L of ice water, continued to freeze and crystallize for 3 hours, and filtered to obtain a yellow solid; the mother liquor was concentrated under reduced pressure to a content of 65% and then applied to the next batch. Dissolve the obtained solid with alkaline water, adjust the pH to 3, add chloroform to extract and remove impurities, continue to add acid to adjust the pH to 1, add dichloromethane to extract, and evaporate the organic layer to dryness to obtain the product 2-thiophene glyoxylic acid with a purity of 98.2% , yield 88%.
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