CN105646124A - Method for catalyzed synthesis of 1,3-butadiyne compound from carboxymethylcellulose/nano-copper in supercritical carbon dioxide - Google Patents
Method for catalyzed synthesis of 1,3-butadiyne compound from carboxymethylcellulose/nano-copper in supercritical carbon dioxide Download PDFInfo
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- CN105646124A CN105646124A CN201610138916.2A CN201610138916A CN105646124A CN 105646124 A CN105646124 A CN 105646124A CN 201610138916 A CN201610138916 A CN 201610138916A CN 105646124 A CN105646124 A CN 105646124A
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- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
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Abstract
The invention discloses a method for catalyzed synthesis of a 1,3-butadiyne compound from carboxymethylcellulose/nano-copper in supercritical carbon dioxide. The method includes sequentially adding end-group alkyne compounds, carboxymethylcellulose/nano-copper and tetrahydrofuran into a high-pressure reactor, sequentially feeding O2 and CO2 into the high-pressure reactor to reach a set pressure, heating to 25-66 DEG C to react by oil bath under electromagnetic stirring, cooling the high-pressure reactor after reaction, releasing gas, desorbing by diethyl ether, filtering to remove undissolved substances, and subjecting filtrate to evaporation and concentration so as to obtain the target product, namely the 1,3-butadiyne compound. The method for catalyzed synthesis of the 1,3-butadiyne compound from the carboxymethylcellulose/nano-copper in the supercritical carbon dioxide is cheap and easily available to a catalysis system, wide in substrate application range and high in total yield.
Description
Technical field
The invention belongs to the oxidative coupling reaction technical field of end-group alkyne compounds, be specifically related to a kind of method that carboxymethyl cellulose/Nanometer Copper catalyzes and synthesizes 1,3-diacetylene compounds in supercritical carbon dioxide.
Background technology
1,3-dialkyne is the important intermediate in natural product synthesis and functional material synthesis. Synthesizing Isosorbide-5-Nitrae-diphenyl-1 first from Glaser in 1869, since 3-diacetylene, the synthetic method of dialkyne is studied widely. High energy medicine, medicine, pesticide, chemical sensor and Minute Organic Synthesis suffer from very big application potential, and its product conjugation diine can play sizable effect as scaffold molecule in many reactions. Between more than 100 year of past, it was found that be much applied to the catalyst system and catalyzing of this this reaction, mainly there are palladium, nickel, copper and gold etc.
Beifuss et al. is using CuCl as catalyst, and air is oxidant, and using DBU as alkali, TMEDA is part, completes the self-coupling reaction of terminal alkyne in acetonitrile. Because aliphatic terminal alkyne does not have the acid strong of aromatic series alkynes, therefore, activity is relatively poor, if replacing DBU with the DABCO of monovalent as alkali, aliphatic terminal alkyne self-coupling reaction yield can improve relatively.
2009, Radivoy et al. finds, even if without other catalyst, oxidant in reaction system, the zerovalent copper nano-particle (CuNPs) in system just can realize end alkynes from coupling, this reaction is all applicable for aliphatic and aromatic terminal alkyne coupling.
Jiang et al. studied and makes Glaser coupling reaction carry out in supercritical carbon dioxide, is solvent with supercritical carbon dioxide and methanol mixed solution, utilizes CuCl2As oxidant, replace the alkali of organic amine with inorganic base sodium acetate, the coupling reaction of multiple Terminal Acetylenes all can have better yield.
2009, Lei group was found that the terminal alkyne coupling reaction of Ni salt catalysis, and this reaction is applicable to the reaction of all kinds of Terminal Acetylenes, and experiment is it is found that realize the asymmetric coupling between different alkynes by changing the mol ratio of alkynes.
2008, Krafft was found that another kind of cobalt catalytic reagent, with Nitrobenzol as oxidant, at 10mol%CoBr2, ZnI2Dialkyne can be obtained when with zinc powder, and yield is higher.
But, in supercritical carbon dioxide, catalyze and synthesize the method for 1,3-diacetylene compounds about carboxymethyl cellulose/Nanometer Copper at present and have no relevant report.
Summary of the invention
Present invention solves the technical problem that there is provided a kind of carboxymethyl cellulose/Nanometer Copper catalyzes and synthesizes 1 in supercritical carbon dioxide, the method of 3-diacetylene compounds, this synthetic method is without part and alkali, in supercritical carbon dioxide, with oxygen for oxidant, end-group alkyne compounds oxidative coupling under the catalyst system and catalyzing of carboxymethyl cellulose/Nanometer Copper is obtained 1,3-diacetylene compounds, wide application range of substrates, yield is better.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, carboxymethyl cellulose/Nanometer Copper catalyzes and synthesizes 1 in supercritical carbon dioxide, the method of 3-diacetylene compounds, it is characterized in that concretely comprising the following steps: in autoclave, be sequentially added into end-group alkyne compounds, carboxymethyl cellulose/Nanometer Copper and oxolane, in autoclave, be then filled with O successively2And CO2To the pressure set, with oil bath heating to 25-66 DEG C of reaction under electromagnetic agitation, after having reacted, autoclave is cooled down, release gas, and use ether desorbing, it is filtered to remove insoluble matter, target product 1 is obtained after filtrate evaporation and concentration, 3-diacetylene compounds, wherein end-group alkyne compounds be phenylacetylene, p-ethyl-phenylacetylene, benzene oxygen propine, to propylbenzene acetylene, to Methoxy-phenylacetylene, to methoxybenzene oxygen propine, to amylbenzene acetylene, m-chloro phenylacetylene, a methylbenzene acetylene, to methylbenzene acetylene or to fluorobenzene acetylene.
It is preferred that, the mol ratio of described end-group alkyne compounds and carboxymethyl cellulose/Nanometer Copper is 1:0.02-0.1.
It is preferred that, the volume that the consumption of described oxolane is 1mmol end-group alkyne compounds correspondence oxolane is 2mL.
It is preferred that, the concrete preparation process of described carboxymethyl cellulose/Nanometer Copper is: take the sodium carboxymethyl cellulose solution that 300mL mass concentration is 1%, and dripping 150mL mass concentration under stirring condition is the CuSO of 10%4Aqueous solution, light blue fluffy solid is had to generate, after centrifuge dehydration colourless to aqueous phase with deionized water wash, be subsequently adding 25mL hydrazine hydrate be stirred at room temperature reaction 3h, obtain aluminium foil paper-like carboxymethyl cellulose/Nanometer Copper by deionized water wash lyophilization to constant weight after centrifuge dehydration.
The present invention compared with prior art has the advantages that catalyst system and catalyzing is cheap and easy to get, and wide application range of substrates, gross production rate is higher.
Detailed description of the invention
By the following examples the foregoing of the present invention being described in further details, but this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to below example, all technology realized based on foregoing of the present invention belong to the scope of the present invention.
Embodiment 1
Take the sodium carboxymethyl cellulose solution 300mL that mass concentration is 1%, under stirring condition, be slowly added dropwise the CuSO that 150mL mass concentration is 10%4Aqueous solution, light blue fluffy solid is had to generate, after centrifuge dehydration colourless to aqueous phase with deionized water wash, add 25mL (excessive) hydrazine hydrate and reaction 3h is stirred at room temperature, after centrifuge dehydration, obtain tinfoil paper paper-like carboxymethyl cellulose/Nanometer Copper catalyst by deionized water wash lyophilization to constant weight.
Embodiment 2
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0063g (0.02mmol), phenylacetylene 0.1020g (1mmol) and oxolane 2mL, in autoclave, is then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 95% by GC.Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.56 (dd, J=9.5Hz, J=1.8Hz, 4H), 7.42-7.35 (m, 6H) ppm.13CNMR(100MHz,CDCl3): ��=132.5,129.3,128.5,121.8,81.6,73.9ppm.
Embodiment 3
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0061g (0.02mmol), p-ethyl-phenylacetylene 0.1311g (1mmol) and oxolane 2mL, in autoclave, is then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 93% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.47 (d, J=8.0Hz, 4H), 7.19 (d, J=8.0Hz, 4H), 2.68 (q, J=8.0Hz, 4H), 1.26 (t, J=8.0Hz, 6H) ppm.13CNMR(100MHz,CDCl3): ��=145.8,132.5,128.1,119.0,81.6,73.5,29.0,15.3ppm.
Embodiment 4
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0061g (0.02mmol), benzene oxygen propine 0.1327g (1mmol) and oxolane 2mL, in autoclave, is then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 89% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.33 (t, J=8.0Hz, 4H), 7.03 (t, J=8.0Hz, 2H), 6.97 (d, J=8.0Hz, 4H), 4.77 (s, 4H) ppm.13CNMR(100MHz,CDCl3): ��=157.4,129.6,121.8,114.9,74.7,71.0,56.2ppm.
Embodiment 5
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0301g (0.1mmol), to propylbenzene acetylene 0.1440g (1mmol) and oxolane 2mL, in autoclave, be then filled with O successively2And CO2To the pressure set, room temperature reaction under electromagnetic agitation, being cooled with an ice bath by autoclave, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter after having reacted, after filtrate evaporation and concentration, the conversion ratio of product measures yield 94% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.44 (d, J=8.0Hz, 4H), 7.15 (d, J=8.0Hz, 4H), 2.60 (t, J=8.0Hz, 4H), 1.69-1.60 (m, 4H), 0.94 (t, J=8.0Hz, 6H) ppm.13CNMR(100MHz,CDCl3): ��=144.3,132.4,128.6,119.0,81.6,73.5,38.1,24.3,13.8ppm.
Embodiment 6
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0061g (0.02mmol), to Methoxy-phenylacetylene 0.1321g (1mmol) and oxolane 2mL, in autoclave, be then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 90% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.46 (d, J=12.0Hz, 4H), 6.85 (d, J=12.0Hz, 4H), 3.82 (s, 6H) ppm.13CNMR(100MHz,CDCl3): ��=160.2,134.1,114.1,113.9,81.3,73.0,55.4ppm.
Embodiment 7
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0152g (0.05mmol), to methoxybenzene oxygen propine 0.1621g (1mmol) and oxolane 2mL, in autoclave, be then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, reactor is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 89% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=6.90 (d, J=12.0Hz, 4H), 6.84 (d, J=8.0Hz, 4H), 4.70 (s, 4H), 3.77 (s, 6H) ppm.13CNMR(100MHz,CDCl3): ��=154.6,151.5,116.2,114.7,74.9,70.9,57.1,55.7ppm.
Embodiment 8
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0061g (0.02mmol), to amylbenzene acetylene 0.1698g (1mmol) and oxolane 2mL, in autoclave, be then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 93% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.46 (d, J=8.0Hz, 4H), 7.17 (d, J=8.0Hz, 4H), 2.62 (t, J=6.0Hz, 4H), 1.66-1.58 (m, 4H), 1.38-1.32 (m, 8H), 0.92 (t, J=6.0Hz, 6H) ppm.13CNMR(100MHz,CDCl3): ��=144.5,132.4,128.6,119.0,81.6,73.5,36.0,31.5,30.9,22.5,14 .0ppm.
Embodiment 9
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0061g (0.02mmol), m-chloro phenylacetylene 0.1373g (1mmol) and oxolane 2mL, in autoclave, is then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 85% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.52 (s, 2H), 7.43 (d, J=8.0Hz, 2H), 7.38 (d, J=8.0Hz, 2H), 7.30 (t, J=6.0Hz, 2H) ppm.13CNMR(100MHz,CDCl3): ��=134.4,132.3,131.1,130.7,129.8,123.3,80.6,74.7ppm.
Embodiment 10
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0061g (0.02mmol), to methylbenzene acetylene 0.1164g (1mmol) and oxolane 2mL, in autoclave, be then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 89% by GC. Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.44 (d, J=8.0Hz, 4H), 7.16 (d, J=8.0Hz, 4H), 2.39 (s, 6H) ppm.13CNMR(100MHz,CDCl3): ��=139.5,132.4,129.3,118.8,81.6,73.5,21.7ppm.
Embodiment 11
High-pressure mini reactor is sequentially added into catalyst carboxymethyl cellulose/Nanometer Copper 0.0061g (0.02mmol), to fluorobenzene acetylene 0.1185g (1mmol) and oxolane 2mL, in autoclave, be then filled with O successively2And CO2To the pressure set, heat to 66 DEG C of reactions with oil bath under electromagnetic agitation, after having reacted, autoclave is cooled with an ice bath, slowly release gas, and use ether desorbing, be filtered to remove insoluble matter, after filtrate evaporation and concentration, the conversion ratio of product measures yield 86% by GC.Its nuclear magnetic data is:1HNMR(400MHz,CDCl3): ��=7.53 (t, J=8.0Hz, 4H), 7.06 (t, J=8.0Hz, 4H) ppm.13CNMR(100MHz,CDCl3): ��=164.3-161.8 (d, J=250Hz), 134.6-134.5 (d, J=10Hz), 117.8,116.0-115.8 (d, J=20Hz), 80.4,73.5ppm.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage; skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; described in above-described embodiment and description is that principles of the invention is described; under the scope without departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements each fall within the scope of protection of the invention.
Claims (4)
1. carboxymethyl cellulose/Nanometer Copper catalyzes and synthesizes 1 in supercritical carbon dioxide, the method of 3-diacetylene compounds, it is characterized in that concretely comprising the following steps: in autoclave, be sequentially added into end-group alkyne compounds, carboxymethyl cellulose/Nanometer Copper and oxolane, in autoclave, be then filled with O successively2And CO2To the pressure set, with oil bath heating to 25-66 DEG C of reaction under electromagnetic agitation, after having reacted, autoclave is cooled down, release gas, and use ether desorbing, it is filtered to remove insoluble matter, target product 1 is obtained after filtrate evaporation and concentration, 3-diacetylene compounds, wherein end-group alkyne compounds be phenylacetylene, p-ethyl-phenylacetylene, benzene oxygen propine, to propylbenzene acetylene, to Methoxy-phenylacetylene, to methoxybenzene oxygen propine, to amylbenzene acetylene, m-chloro phenylacetylene, a methylbenzene acetylene, to methylbenzene acetylene or to fluorobenzene acetylene.
2. carboxymethyl cellulose/Nanometer Copper according to claim 1 catalyzes and synthesizes 1 in supercritical carbon dioxide, the method of 3-diacetylene compounds, it is characterised in that: the mol ratio of described end-group alkyne compounds and carboxymethyl cellulose/Nanometer Copper is 1:0.02-0.1.
3. carboxymethyl cellulose/Nanometer Copper according to claim 1 catalyzes and synthesizes 1 in supercritical carbon dioxide, the method of 3-diacetylene compounds, it is characterised in that: the volume that the consumption of described oxolane is 1mmol end-group alkyne compounds correspondence oxolane is 2mL.
4. carboxymethyl cellulose/Nanometer Copper according to claim 1 catalyzes and synthesizes 1 in supercritical carbon dioxide, the method of 3-diacetylene compounds, it is characterized in that the concrete preparation process of described carboxymethyl cellulose/Nanometer Copper is: take the sodium carboxymethyl cellulose solution that 300mL mass concentration is 1%, dripping 150mL mass concentration under stirring condition is the CuSO of 10%4Aqueous solution, light blue fluffy solid is had to generate, after centrifuge dehydration colourless to aqueous phase with deionized water wash, be subsequently adding 25mL hydrazine hydrate be stirred at room temperature reaction 3h, obtain aluminium foil paper-like carboxymethyl cellulose/Nanometer Copper by deionized water wash lyophilization to constant weight after centrifuge dehydration.
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| CN109225223A (en) * | 2018-08-30 | 2019-01-18 | 济南大学 | A kind of preparation of copper cobalt support type grapheme material and the application in catalysis Glaser coupling reaction |
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| CN105016947A (en) * | 2015-07-15 | 2015-11-04 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN105153051A (en) * | 2015-08-31 | 2015-12-16 | 河南师范大学 | Method for catalytically synthesizing 1, 2, 3-triazole compounds by aid of carboxymethyl cellulose/nanometer copper |
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| CN105016947A (en) * | 2015-07-15 | 2015-11-04 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN105153051A (en) * | 2015-08-31 | 2015-12-16 | 河南师范大学 | Method for catalytically synthesizing 1, 2, 3-triazole compounds by aid of carboxymethyl cellulose/nanometer copper |
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| HUAN-FENG JIANG ET AL.: "Cu(II)-Promoted Oxidative Homocoupling Reaction of Terminal Alkynes in Supercritical Carbon Dioxide", 《SYNTHESIS》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225223A (en) * | 2018-08-30 | 2019-01-18 | 济南大学 | A kind of preparation of copper cobalt support type grapheme material and the application in catalysis Glaser coupling reaction |
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