CN113149827A - Method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide - Google Patents
Method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide Download PDFInfo
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- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- 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
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Abstract
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide. The method comprises the following stepsComprises the following steps: adding alkyne, alkali and solvent into a reaction tube, wherein the alkyne is used as a raw material, the alkali and the solvent provide a strong alkaline environment, introducing CO into a reaction container2Forming a carbon dioxide atmosphere, heating and stirring for reaction, cooling to room temperature after the reaction is finished, extracting and separating liquid, acidifying a water layer, and then further separating and purifying to obtain the alkynoic acid compound. The method is carried out under the conditions of low temperature and normal pressure, does not need to add a metal catalyst, has single product, is convenient to separate, has good substrate applicability and safe and simple operation, and has potential industrial application prospect and good economic benefit.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing alkynoic acid by direct carboxylation of terminal alkyne and carbon dioxide under mild conditions.
Background
With the continued use of fossil fuels, CO2The gradual increase of the content causes global greenhouse effect and causes a series of climate, environmental and ecological problems (M.Ding, R.W.Flaig, H.L.Jiang, O.M.Yaghi, chem.Soc.Rev.2019,48, 2783-. At the same time, CO2Not only is the main component of greenhouse gas, but also is used as C which has large storage capacity, no toxicity, low price, easy obtainment and regeneration1Resources, which are of great importance for their efficient use and conversion into fine chemicals with high added values (J.Artz, T.E.Muller, K.Thenert, J.Kleinekorete, R.Meys, A.Sternberg, A.Bardow, W.Leitner, chem.Rev.2018,118, 434-504; Q.Liu, L.Wu, R.Jacksell, M.Beller, nat.Commun.2015,6, 5933-5948; M.Kapoor, D.Liu, M.C.Yoourg, J.Am.Chem.Soc.2018,140, 6818-6822.).
Alkynes are important starting materials in organic synthesis due to their special properties and ready availability. Alkyne can provide a plurality of compounds with important industrial application through functionalization, and is one of important research fields in modern synthetic chemistry. The direct carboxylation of carbon dioxide and terminal alkynes to synthesize alkynoic acids is an effective method for utilizing carbon dioxide, because alkynoic acids are important intermediates for synthesizing drugs and fine chemicals (W.Xiong, F.Shi, R.Cheng, B.Zhu, L.Wang, P.Chen, H.Lou, W.Wu, C.Qi, M.Lei, H.Jiang, ACS Catal.2020,10, 7968-doped 7978; K.Sekine, T.Yamada, Chem.Soc.Rev.2016,45, 4524-doped 4532; J.Jover, F.Maseras, J.org.Chem.2014,79, 11981-doped 11987).
However, due to CO2Chemical stability and kinetic inertness of the catalyst itself, it has been reported that methods for the synthesis of alkynoic acids using carbon dioxide and terminal alkynes often require large amounts of water and air sensitive organic reagents such as grignard reagents and organolithium reagents (a. corea, r. mart i n, angelw.chem.int.ed.2009, 48, 6201-. In recent years, in order to solve the problems of difficult recovery of the noble metal catalyst, etc., some heterogeneous catalysts have been used for the reaction. Different catalyst carriers such as metal organic frameworks (X.Liu, J.Ma, Z.Niu, G.Yang, P.Cheng, Angew.chem.int.Ed.2015,54, 988. H.991; R.A.Molla, K.Ghosh, B.Banerjee, M.A.Iquubal, S.K.Kundi, S.M.Islam, A.Bhaunik, J.Colloid. Sci.2016,477, 220-229; M.Trivedi, B.Bhaskaaraman, A.Chemar, G.Singh, A.Kumar, N.P.Rath, New J.chem.2016,40,3109- -3118; N.Zhang, X.Liu, T.Li, J.J.Yang, Yang.Yang, G.20111, N.P.J.J.D.20111, J.J.J.J.S.J.H.S.J.J.H.D.S.S.S.H.20111, U.J.S.J.H.S. H.S. H.D. H.7, S. J. H.S. K. H. 120, S. K. H. K. 120, S. H. K. H. K. H. K. 19, S. H. K. H. K. H. 19, S. K. 120, S. K. H. 120, S. H. K. H. S. H. S. H. S. H. S. H. S. H. S. H. S. K. S. K. S. K. S. H. S. K. S. S, 12, 1055-; U.S. Gulati, U.S. Chinna RajeshD.S. Rawat, J.M.Zaleski, Green chem.2020,22,3170-2And other materials such as Cu nanomaterials (P.Yang, S.Zuo, F.Zhang, B.Yu, S.Guo, X.Yu, Y.Zhao, J.Zhang, Z.Liu, Ind.Eng.Chem.Res.2020,59,7327-7335), ionic liquids (A.A.Chaugule, A.H.Tamboli, H.Kim, chem.Eng.J.2017,326,1009-1019) are also used for the reaction. There are also reports of silane-mediated carboxylation reactions catalyzed by potassium tert-butoxide (B.Yu, P.Yang, X.Gao, Z.Yang, Y.ZHao, H.Zhang, Z.Liu, Sci.China chem.2018,61, 449-456); bao and coworkers use quaternary ammonium salts and inorganic bases as new strategies for carboxylation of terminal alkynes with carbon dioxide in low boiling solvents, but the reaction has to be carried out at high pressure and quaternary ammonium salts are required as additives (w.wang, x.feng, k.sui, d.fang, m.bao, j.co.2Util.2019,32,140-145)。
In summary, although many methods for synthesizing alkynoic acids by using carbon dioxide are reported, practical application of the methods is still difficult due to severe reaction conditions, complex catalyst synthesis, high catalytic cost and the like. Therefore, a direct utilization of CO under mild conditions was developed2The carboxylation with terminal alkynes is still of great importance.
Disclosure of Invention
In order to overcome the difficulties presented above, it is an object of the present invention to provide a process for the synthesis of alkynoic acids using terminal alkynes with carbon dioxide.
The invention provides a method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide. The method takes alkyne as raw material to react with CO under the alkaline condition2And carrying out direct carboxylation reaction to obtain the alkynoic acid compound.
The purpose of the invention is realized by at least one of the following technical solutions.
The method provided by the invention comprises the steps of adding a solvent, alkyne and alkali into a reactor to obtain a mixed solution, introducing CO into a reaction container, wherein the alkyne in the mixed solution is used as a raw material2Heating and stirring, cooling to room temperature after reaction, and adding waterAnd extracting and separating by ethyl acetate, acidifying a water layer, and further separating and purifying to obtain the alkynoic acid compound.
The method for synthesizing the alkynoic acid by utilizing the terminal alkyne and the carbon dioxide has the chemical reaction equation as follows:
wherein R is one of phenyl, p-tolyl, p-ethylphenyl, p-propylphenyl, p-pentylphenyl, m-tolyl, m-fluorophenyl, m-chlorophenyl, m-bromophenyl, o-bromophenyl, p-methoxyphenyl, p-ethoxyphenyl, p-pentyloxyphenyl, 3, 5-dimethoxyphenyl, p-cyanophenyl, 3, 5-bis (trifluoromethyl) phenyl, phenoxy, 1-naphthyl, 2-naphthyl, 4-biphenyl, 6-methoxy-2-naphthyl, 3-thienyl, p-ethynylphenyl.
The above-mentioned
Is one of phenylacetylene, 4-methylacetylene, 4-ethylphenylacetylene, 4-propylphenylacetylene, 4-pentylphenylacetylene, 3-methylphenylacetylene, 1-ethynyl-3-fluorobenzene, 3-chlorophenylacetylene, 3-bromophenylacetylene, 2-bromophenylacetylene, (4-bromophenyl) acetylene, 4-ethynylanisole, 4-ethynylphenetole, 4-ethynylphenylpentyl ether, 3, 5-dimethoxyphenylacetylene, 4-ethynylbenzonitrile, 3, 5-bis (trifluoromethyl) phenylacetylene, phenylpropyl ether, 1-ethynylnaphthalene, 2-ethynylnaphthalene, 4-ethynylbiphenyl, 2-ethynyl-6-methoxynaphthalene, 3-ethynylthiophene, 1, 4-diethynylbenzene.
The invention provides a method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide, which comprises the following steps:
(1) adding alkyne, alkali and an organic solvent into a reaction container, uniformly mixing, heating and stirring under the atmosphere of carbon dioxide, and cooling to room temperature after the reaction is finished to obtain a reaction solution;
(2) and (2) extracting the reaction liquid obtained in the step (1), separating liquid, taking a water layer, acidifying, separating and purifying to obtain the alkynoic acid.
Further, the organic solvent in the step (1) is one of dimethyl sulfoxide (DMSO), N-dimethylformamide, N-methylpyrrolidone and acetonitrile.
Further, the base in the step (1) is one of cesium carbonate, potassium tert-butoxide, 4-dimethylaminopyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, potassium carbonate and sodium hydroxide.
Preferably, the base of step (1) is cesium carbonate.
Further, the molar ratio of the base to the alkyne in the step (1) is 1.5-2.5: 1; the alkyne has a structural formula of
Preferably, the molar ratio of base to alkyne in step (1) is 2: 1.
Further, the temperature of the heating and stirring treatment in the step (1) is 40-70 ℃.
Preferably, the temperature of the heating and stirring treatment in the step (1) is 60-70 ℃.
Further preferably, the temperature of the heating and stirring treatment in the step (1) is 60 ℃.
Further, the time of the heating and stirring treatment in the step (1) is 3-36 h.
Preferably, the heating and stirring treatment time of the step (1) is 6-36 h.
Further preferably, the time of the heating and stirring treatment in the step (1) is 18-24 h.
Still more preferably, the time of the heating and stirring treatment in the step (1) is 24 h.
Further, the stirring speed of the heating and stirring treatment in the step (1) is 600-800 rpm.
Preferably, in step (1), carbon dioxide may be charged into the reaction vessel by three gas exchanges to form a carbon dioxide atmosphere.
Preferably, in the step (1), the reaction vessel may be evacuated and then carbon dioxide may be introduced to form a carbon dioxide atmosphere.
Preferably, in step (1), CO is introduced2The pressure in the post-reaction vessel is 1-2 atmospheres.
Further, the extraction in the step (2) comprises the following steps: adding water into the reaction solution obtained in the step (1), extracting with ethyl acetate, and standing for liquid separation to obtain a water layer and an organic layer; the acidification comprises the following steps: adjusting the pH value of the water layer to be acidic to obtain an acidified water layer; the separation and purification comprises the following steps: and extracting the acidified water layer with ethyl acetate again, separating liquid, taking an organic layer, washing the organic layer with saturated saline solution, drying, filtering to obtain filtrate, and concentrating under reduced pressure to obtain a pure product, namely the acetylenic acid.
Preferably, after the reaction is finished, cooling to room temperature, adding NaOH solution (sodium hydroxide solution is added to change more alkynoic acid into salt so as to improve the extraction yield, and the NaOH solution can be added or not added), and then adding H2And O, adding ethyl acetate for extraction for 4 times, removing an organic layer, taking a water layer, adding an HCl solution into the water layer to adjust the pH value to 1, then adding ethyl acetate for extraction for 4 times again, removing the water layer, washing the organic layer with saturated saline solution for 2 times, drying with anhydrous magnesium sulfate, performing suction filtration, and concentrating under reduced pressure to obtain the alkynoic acid.
Further, the pH of the acidified aqueous layer was 1.0.
Preferably, the pH of the aqueous layer may be adjusted to acidity using hydrochloric acid having a concentration of 2 mol/L.
In the method provided by the invention, when the alkali in the step (1) is cesium carbonate, the heating and stirring treatment temperature is 60-70 ℃, and the heating and stirring treatment time is 18-24h, the yield of the alkynoic acid can reach more than 80%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the method for synthesizing the alkynoic acid by utilizing the terminal alkyne and the carbon dioxide is different from the traditional method for synthesizing the alkynoic acid compound, the traditional method for synthesizing the alkynoic acid compound needs to add strong nucleophilic reagents such as a green reagent and the like, and the reaction conditions are severe or a noble metal catalyst needs to be added; the synthesis method has the advantages of mild reaction conditions, no metal catalyst, single product, easiness in separation, safety and simplicity in operation and the like, and meanwhile, the method provided by the invention is high in yield and wide in substrate applicability (namely, the method can be suitable for synthesis of various acetylenic acids); wherein, the yield of most substrates is higher, and the method has certain industrial production application prospect and good economic benefit.
Drawings
FIGS. 1 and 2 are a hydrogen spectrum and a carbon spectrum of the objective products obtained in examples 1 to 13, respectively;
FIGS. 3 and 4 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 14, respectively;
FIGS. 5 and 6 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 15, respectively;
FIGS. 7 and 8 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 16, respectively;
FIGS. 9 and 10 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 17;
FIGS. 11 and 12 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 18;
FIGS. 13 and 14 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 19;
FIGS. 15 and 16 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 20;
FIGS. 17 and 18 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 21;
fig. 19 and 20 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 22, respectively.
Fig. 21 and 22 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 23, respectively.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, the stirring is stopped, the reaction solution is cooled to room temperature, 5 ml of 2mol/L sodium hydroxide solution is added into the reaction solution, 5 ml of water is added, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated common salt water and dried on magnesium sulfate, filtrate is taken by filtration, and reduced pressure concentration is carried out to obtain the target product, wherein the yield is 96%.
Example 2
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 1.5 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, the stirring is stopped, the reaction solution is cooled to room temperature, 5 ml of 2mol/L sodium hydroxide solution is added into the reaction solution, 5 ml of water is added, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, liquid separation is carried out, an organic layer is taken, the organic layer is washed by using saturated salt and dried on magnesium sulfate, filtrate is taken by filtration, and reduced pressure concentration is carried out to obtain the target product, wherein the yield is 80%.
Example 3
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2.5 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 97%.
Example 4
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of potassium tert-butoxide into a reaction tube, pumping the reaction tube for 3 times, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 27%.
Example 5
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of 1, 8-diazabicycloundec-7-ene are added into a reaction tube, the reaction tube is pumped and ventilated for 3 times, and CO is charged2Is charged with the CO2Stirring the reaction solution at 60 deg.C under carbon dioxide atmosphere at 1 atm for 24 hr at 800rpm, cooling to room temperature, adding water, extracting with ethyl acetate for 4 times, separating, collecting water layer, acidifying the water layer with 2mol/L hydrochloric acid to pH 1, extracting with ethyl acetate, collecting organic layer, and washing the organic layer with saturated salt solutionAnd dried over magnesium sulfate, filtered to take the filtrate, and concentrated under reduced pressure to obtain the target product with a yield of 13%.
Example 6
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 40 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 48%.
Example 7
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube was 1 atm, the reaction was stirred at 50 ℃ for 24 hours in a carbon dioxide atmosphere at a stirring speed of 800rpm, the stirring was stopped, the reaction solution was cooled to room temperature, water was added to the reaction solution, extraction was performed 4 times with ethyl acetate, liquid separation was performed, a water layer was taken, the water layer was acidified to pH 1 with 2mol/l hydrochloric acid, extraction was performed with ethyl acetate, an organic layer was taken, the organic layer was washed with saturated brine and dried over magnesium sulfate, filtrate was taken by filtration, and concentration was performed under reduced pressure to obtain the target product with a yield of 83%.
Example 8
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate are added into a reaction tube, and the reaction tube is pumped and ventilated for 3 times and is filled with gasCO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 70 ℃, the stirring speed is 800rpm, the stirring is stopped, the reaction solution is cooled to room temperature, water is added into the reaction solution, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to the pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 92%.
Example 9
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
4 ml of N, N-dimethylformamide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate are added into a reaction tube, the reaction tube is pumped and ventilated for 3 times, and CO is filled2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 27%.
Example 10
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2Stirring the reaction solution at 60 deg.C for 6 hr under carbon dioxide atmosphere at 800rpm, stopping stirring, cooling to room temperature, adding water, extracting with ethyl acetate for 4 times, separating, collecting water layer, acidifying the water layer with 2mol/L hydrochloric acid to pH 1, extracting with ethyl acetate, collecting organic layer, washing with saturated salt water, and adding sulfuric acidDrying on magnesium, filtering to obtain filtrate, and concentrating under reduced pressure to obtain the target product with the yield of 80%.
Example 11
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 12 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, the stirring is stopped, the reaction solution is cooled to room temperature, water is added into the reaction solution, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to the pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 84%.
Example 12
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 18 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 91%.
Example 13
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 30 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 96%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the examples 1-13 are respectively shown in fig. 1 and fig. 2, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3):δ＝10.74(s,1H),7.61(d,J＝7.6Hz,2H),7.48(t,J＝7.2Hz,1H),7.39(t,J＝7.6Hz,2H).
13C NMR(100MHz,CDCl3):δ＝158.97,133.35,131.23,128.72,119.09,89.21,80.17.
IR(KBr):2209,1672,1414,1303,1204,917,746,610cm-1.
the structure of the target product was deduced from the above data as follows:
example 14
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of 4-methylphenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube into the reaction tube for 3 times of ventilation, and filling CO into the reaction tube2Is charged with the CO2The gas pressure of the back reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, the stirring is stopped, the reaction solution is cooled to the room temperature, 5 ml of 2mol/L sodium hydroxide solution is added into the reaction solution, 5 ml of water is added, extraction is carried out for 4 times by ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to the pH value of 1 by 2mol/L hydrochloric acid, and then acetic acid B is usedThe ester was extracted, and the organic layer was washed with saturated brine and dried over magnesium sulfate, and the filtrate was filtered and concentrated under reduced pressure to obtain the objective product with a yield of 94%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 3 and 4, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝7.48(d,J＝8.0Hz,2H),7.24(d,J＝8.0Hz,2H),2.32(s,3H).
13C NMR(100MHz,DMSO):δ＝154.85,141.58,133.01,130.08,116.39,85.31,81.91,21.62.
IR(KBr):2199,1671,1406,1295,1204,906,814,601cm-1.
the structure of the target product is deduced from the above data as follows:
example 15
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of 3-bromophenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 90%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 5 and 6, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝7.77(t,J＝1.6Hz,1H),7.70–7.67(m,1H),7.60–7.58(m,1H),7.37(t,J＝8.0Hz,1H).
13C NMR(100MHz,DMSO):δ＝154.51,135.07,134.23,132.01,131.39,122.29,121.72,83.10,82.85.
IR(KBr):2922,1643,1377,1259,1173,760,587cm-1.
the structure of the target product is deduced from the above data as follows:
example 16
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of 3, 5-dimethoxyphenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube was 1 atm, the reaction was stirred at 60 ℃ for 24 hours in a carbon dioxide atmosphere at a stirring speed of 800rpm, the stirring was stopped, the reaction solution was cooled to room temperature, water was added to the reaction solution, extraction was performed 4 times with ethyl acetate, liquid separation was performed, a water layer was taken, the water layer was acidified to pH 1 with 2mol/l hydrochloric acid, extraction was performed with ethyl acetate, an organic layer was taken, the organic layer was washed with saturated saline and dried over magnesium sulfate, filtrate was taken by filtration, and concentration was performed under reduced pressure to obtain the objective product with a yield of 86%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 7 and fig. 8, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝6.73(d,J＝2.0Hz,2H),6.62(t,J＝2.4Hz,1H),3.74(s,6H).
13C NMR(100MHz,DMSO):δ＝160.93,154.70,120.85,110.54,104.21,84.82,81.60,55.88.
IR(KBr):2920,2207,1668,1589,1264,819cm-1.
the structure of the target product is deduced from the above data as follows:
example 17
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
4 ml of dimethyl sulfoxide, 1 mmol of 4-ethynylbenzonitrile and 2 mmol of cesium carbonate are added into a reaction tube, the reaction tube is pumped and ventilated for 3 times, and CO is filled2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 82%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 9 and fig. 10, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝7.89(d,J＝8.0Hz,2H),7.77(d,J＝8.0Hz,2H).
13C NMR(100MHz,DMSO):δ＝154.34,133.62,133.17,124.30,118.48,113.48,84.99,82.56.
IR(KBr):2916,2198,1686,1595,1371,1278,1204,837,557cm-1.
the structure of the target product is deduced from the above data as follows:
example 18
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 3, 5-bis (trifluoromethyl) phenylacetylene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 89%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 11 and fig. 12, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝8.22(s,2H),8.09(s,1H).
13C NMR(100MHz,DMSO):δ＝154.15,133.30,133.27,133.23,132.01,131.68,131.34,131.01,127.07,124.36,124.13,124.10,124.06,122.49,121.65,118.93,84.37,80.62.
IR(KBr):2547,2225,1676,1383,1271,1125,679cm-1.
the structure of the target product is deduced from the above data as follows:
example 19
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
4 ml of dimethyl sulfoxide, 1 mmol of 3-ethynylthiophene and 2 mmol of cesium carbonate are added into a reaction tube, the reaction tube is pumped and ventilated for 3 times, and CO is filled2Is charged with the CO2Stirring the reaction solution at 60 deg.C for 24 hr under carbon dioxide atmosphere at 800rpm, stopping stirring, cooling to room temperature, adding water, extracting with ethyl acetate for 4 times, separating, collecting water layer, acidifying the water layer with 2mol/L hydrochloric acid to pH 1, extracting with ethyl acetate, collecting organic layer, washing with saturated salt water, drying over magnesium sulfate, filtering to obtain filtrateAnd concentrating under reduced pressure to obtain the target product with the yield of 92%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 13 and fig. 14, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝8.10(dd,J＝1.2,3.2Hz,1H),7.61(dd,J＝2.8,4.8Hz,1H),7.27(dd,J＝1.2,4.8Hz,1H).
13C NMR(100MHz,DMSO):δ＝154.92,135.12,130.34,128.04,118.46,82.11,80.81.
IR(KBr):1655,1260,873,764,599.cm-1.
the structure of the target product is deduced from the above data as follows:
example 20
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of 1, 4-diacetylene benzene and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times of ventilation, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube was 1 atm, the reaction was stirred at 60 ℃ for 24 hours in a carbon dioxide atmosphere at a stirring speed of 800rpm, the stirring was stopped, the reaction solution was cooled to room temperature, water was added to the reaction solution, extraction was performed 4 times with ethyl acetate, liquid separation was performed, a water layer was taken, the water layer was acidified to pH 1 with 2mol/l hydrochloric acid, extraction was performed with ethyl acetate, an organic layer was taken, the organic layer was washed with saturated saline and dried over magnesium sulfate, filtrate was taken by filtration, and concentration was performed under reduced pressure to obtain the objective product at a yield of 81%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 15 and fig. 16, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝7.67(s,4H).
13C NMR(100MHz,DMSO):δ＝154.50,133.37,121.63,84.31,83.48.
IR(KBr):2206,1597,1378,1271,1200,839,738,667cm-1.
the structure of the target product is deduced from the above data as follows:
example 21
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
adding 4 ml of dimethyl sulfoxide, 1 mmol of 4-acetylene biphenyl and 2 mmol of cesium carbonate into a reaction tube, pumping the reaction tube for 3 times, and introducing CO2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 83%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 17 and fig. 18, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝7.67(s,4H).
13C NMR(100MHz,DMSO):δ＝154.50,133.37,121.63,84.31,83.48.
IR(KBr):2206,1597,1378,1271,1200,839,738,667cm-1.
the structure of the target product is deduced from the above data as follows:
example 22
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
4 ml of dimethyl sulfoxide, 1 mmol of 1-ethynylnaphthalene and 2 mmol of cesium carbonate are added into a reaction tube, the reaction tube is pumped and ventilated for 3 times, and CO is filled2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmosphere, stirring reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 ℃, the stirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH value of 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated salt water and dried on magnesium sulfate, filtrate is obtained by filtration, and reduced pressure concentration is carried out to obtain a target product, wherein the yield is 95%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 19 and fig. 20, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝8.22(d,J＝8.4Hz,1H),8.06(d,J＝8.4Hz,1H),7.97(d,J＝8.0Hz,1H),7.89(d,J＝6.8Hz,1H),7.67(t,J＝7.2Hz,1H),7.58(t,J＝7.6Hz,1H),7.53(t,J＝7.6Hz,1H).
13C NMR(100MHz,DMSO):δ＝154.89,133.30,133.27,133.12,131.81,129.19,128.43,127.54,125.99,125.31,116.83,86.98,82.95.
IR(KBr):2928,2205,1677,1504,1295,1214,769cm-1.
the structure of the target product is deduced from the above data as follows:
example 23
A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide comprises the following steps:
4 ml of dimethyl sulfoxide, 1 mmol of phenylpropargyl ether and 2 mmol of cesium carbonate are added to a reaction tube, the reaction tube is pumped with gas for 3 times, and CO is introduced2Is charged with the CO2The gas pressure of the post-reaction tube is 1 atmospheric pressure, and the reaction is carried out for 24 hours under the conditions of carbon dioxide atmosphere and 60 DEG CStirring speed is 800rpm, stirring is stopped, cooling is carried out to room temperature, water is added into reaction liquid, extraction is carried out for 4 times by using ethyl acetate, liquid separation is carried out, a water layer is taken, the water layer is acidified to pH 1 by using 2mol/L hydrochloric acid, extraction is carried out by using ethyl acetate, an organic layer is taken, the organic layer is washed by using saturated common salt and dried over magnesium sulfate, filtrate is obtained by filtration, and concentration under reduced pressure is carried out to obtain a target product, wherein the yield is 85%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 21 and 22, and the structural characterization data are shown as follows:
1H NMR(400MHz,DMSO):δ＝7.35–7.29(m,1H),7.01–6.97(m,2H),5.01(s,1H).
13C NMR(100MHz,DMSO):δ＝157.44,154.08,130.05,122.02,115.19,82.29,79.78,55.42,21.46.
IR(KBr):2245,1680,1420,1287,1226,895,748,610cm-1
the structure of the target product is deduced from the above data as follows:
it should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for synthesizing alkynoic acid by utilizing terminal alkyne and carbon dioxide is characterized in that the chemical reaction equation is as follows:
wherein R is one of phenyl, p-tolyl, p-ethylphenyl, p-propylphenyl, p-pentylphenyl, m-tolyl, m-fluorophenyl, m-chlorophenyl, m-bromophenyl, o-bromophenyl, p-methoxyphenyl, p-ethoxyphenyl, p-pentyloxyphenyl, 3, 5-dimethoxyphenyl, p-cyanophenyl, 3, 5-bis (trifluoromethyl) phenyl, phenoxy, 1-naphthyl, 2-naphthyl, 4-biphenyl, 6-methoxy-2-naphthyl, 3-thienyl, p-ethynylphenyl.
2. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 1, which comprises the following steps:
(1) adding alkyne, alkali and an organic solvent into a reaction vessel, uniformly mixing, heating and stirring under the atmosphere of carbon dioxide, and cooling to room temperature to obtain a reaction solution;
(2) and (2) extracting the reaction liquid obtained in the step (1), separating liquid, taking a water layer, acidifying, separating and purifying to obtain the alkynoic acid.
3. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 2, wherein the organic solvent in step (1) is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and acetonitrile.
4. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 2, wherein the base in step (1) is one of cesium carbonate, potassium tert-butoxide, 4-dimethylaminopyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, potassium carbonate and sodium hydroxide.
5. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 2, wherein the molar ratio of the base to the alkyne in the step (1) is 1.5-2.5: 1; the alkyne has a structural formula of
6. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 2, wherein the temperature of the heating and stirring treatment in the step (1) is 40-70 ℃.
7. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 2, wherein the heating and stirring treatment time in step (1) is 6-36 h.
8. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 2, wherein the stirring speed of the heating and stirring treatment in step (1) is 600-800 rpm.
9. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in any one of claims 2 to 8, wherein the extracting in the step (2) comprises: adding water into the reaction solution obtained in the step (1), extracting with ethyl acetate, separating liquid, and taking a water layer; the acidification comprises the following steps: adjusting the pH value of the water layer to be acidic to obtain an acidified water layer; the separation and purification comprises the following steps: and extracting the acidified water layer with ethyl acetate again, separating liquid, taking an organic layer, washing the organic layer with saturated saline, drying, filtering to obtain filtrate, and concentrating under reduced pressure to obtain the acetylenic acid.
10. The method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide as claimed in claim 9, wherein the pH of the acidified water layer is 1.0.
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