CN114522668B - Application of ethoxy column [6] arene crystal material in selective adsorption of tetrahydropyrrole - Google Patents
Application of ethoxy column [6] arene crystal material in selective adsorption of tetrahydropyrrole Download PDFInfo
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- CN114522668B CN114522668B CN202210035631.1A CN202210035631A CN114522668B CN 114522668 B CN114522668 B CN 114522668B CN 202210035631 A CN202210035631 A CN 202210035631A CN 114522668 B CN114522668 B CN 114522668B
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- tetrahydropyrrole
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- tetrahydrofuran
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- ethoxy
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 239000013078 crystal Substances 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 69
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 67
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 title claims abstract description 60
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 98
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000002178 crystalline material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- -1 N-methyltetrazole Chemical compound 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004176 ammonification Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000003988 headspace gas chromatography Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- IRHZSUFOQLAHDV-UHFFFAOYSA-N 1-(2-methylpropyl)tetrazole Chemical compound CC(C)CN1C=NN=N1 IRHZSUFOQLAHDV-UHFFFAOYSA-N 0.000 description 1
- ZDPACSAHMZADFZ-UHFFFAOYSA-N 1-[3-(2,4,6-Trimethoxybenzoyl)propyl]pyrrolidinium chloride Chemical compound [Cl-].COC1=CC(OC)=CC(OC)=C1C(=O)CCC[NH+]1CCCC1 ZDPACSAHMZADFZ-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- OMAFFHIGWTVZOH-UHFFFAOYSA-N 1-methyltetrazole Chemical compound CN1C=NN=N1 OMAFFHIGWTVZOH-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 description 1
- XUKUURHRXDUEBC-UHFFFAOYSA-N Atorvastatin Natural products C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CCC(O)CC(O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PWACSDKDOHSSQD-IUTFFREVSA-N acrivastine Chemical compound C1=CC(C)=CC=C1C(\C=1N=C(\C=C\C(O)=O)C=CC=1)=C/CN1CCCC1 PWACSDKDOHSSQD-IUTFFREVSA-N 0.000 description 1
- 229960003792 acrivastine Drugs 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229960005370 atorvastatin Drugs 0.000 description 1
- 229960004156 bepridil hydrochloride Drugs 0.000 description 1
- JXBBWYGMTNAYNM-UHFFFAOYSA-N bepridil hydrochloride Chemical compound [H+].[Cl-].C1CCCN1C(COCC(C)C)CN(C=1C=CC=CC=1)CC1=CC=CC=C1 JXBBWYGMTNAYNM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229960002113 buflomedil hydrochloride Drugs 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
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Abstract
The application discloses an ethoxy column [6]]Application of arene crystal material in selective adsorption of tetrahydropyrrole, and ethoxy column [6]]The structural formula of the aromatic hydrocarbon crystal material is as follows:the application also discloses a separation method of the tetrahydropyrrole and the tetrahydrofuran, which utilizes the ethoxy column [6]]The arene crystal material adsorbs and separates the mixture of the tetrahydropyrrole and the tetrahydrofuran. The separation process is simple to operate, does not need complex equipment, and has good operation safety; the separation does not need rectification operation, so that energy sources are saved, and the production cost is reduced; the used crystal material has high stability, can be recycled, and the separation effect is not reduced.
Description
Technical Field
The application relates to the field of adsorption separation, in particular to application of an ethoxy column [6] arene crystal material in selective adsorption of tetrahydropyrrole.
Background
Tetrahydropyrrole is an intermediate for producing a series of medical products such as buflomedil hydrochloride (Bulglomedil Hydrochloride), benpridil hydrochloride (Bepridil Hydrochloride), atorvastatin (Acrivastine) and the like. The synthesis method reported in the literature mainly comprises the following steps: catalytic hydrogenation processes (Journal of the Amertican Chemical Society,131 (16), 5812-5822; 2009) starting from pyrrole or dihydropyrrole; a method of catalyzing cyclization by using succinimide or pyrrolidone as a raw material [ Chemistry & Industry (London, united Kingdom), (17), 547-8;1990];1, 4-butanediol high temperature high pressure ammonification cyclization process [ J.org. chem,1994,59 (14), 3998] and tetrahydrofuran catalytic ammonification process [ Journal of Catalysis,1974,35:325-329].
Currently, industrial tetrahydropyrrole is mainly obtained by a tetrahydrofuran catalytic ammonification method, which comprises catalytic ammonification, rectification purification and molecular sieve drying. However, in the production process of tetrahydropyrrole, due to the limitation of the conversion rate and the molar yield, part of the raw material tetrahydrofuran and by-products including N-methyltetrazole, N-N-butyltetrahydropyrrole, N-isobutyltetrazole and the like are always remained. The presence of these by-products not only severely affects the smell and acid wash colorimetry of the tetrahydropyrrole, but also limits its further processing utilization. Since the boiling point of tetrahydropyrrole (87.0 ℃) is close to that of tetrahydrofuran (67.0 ℃) and that of N-methyl-tetrahydropyrrole (81.0 ℃), these impurities are difficult to remove, resulting in the purity of the tetrahydropyrrole being affected. Therefore, how to separate impurities such as the tetrahydropyrrole, the tetrahydrofuran and the like becomes a key link for purifying the tetrahydropyrrole.
Chinese patent publication No. CN 101948448A discloses a method for preparing and purifying tetrahydropyrrole. The patent firstly uses ZSM-5 molecular sieve as adsorbent to replace the original filler in the rectifying tower, then makes the liquid phase form of the produced crude product of the pyrrolidine enter the tower kettle of the rectifying tower to carry out normal pressure continuous rectification, and receives the fraction at 86-87 ℃. The method can better remove most of harmful impurities and improve the purity of the tetrahydropyrrole.
However, the temperature required in the rectification process of the method is high, and huge energy consumption is required, so that the method is unfavorable for the development of green energy in China; and the maintenance cost of the rectification equipment is high, the production cost of enterprises is increased, and the economic benefit of the enterprises is reduced.
In view of the above, finding a new method for effectively separating pyrrolidine from tetrahydrofuran with less energy consumption is a key point for purifying the pyrrolidine in the industry at present.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the application provides the application of the ethoxy column [6] arene crystal material in selectively adsorbing the tetrahydropyrrole, the high-selectivity adsorption of the tetrahydropyrrole can be realized at normal temperature, and then the high-purity tetrahydropyrrole can be obtained by heating and desorption.
The application of the ethoxy column [6] arene crystal material in selectively adsorbing the tetrahydropyrrole is characterized in that the structural formula of the ethoxy column [6] arene crystal material is as follows:
the application also provides a separation method of the tetrahydropyrrole and the tetrahydrofuran, which utilizes the ethoxy column [6] arene crystal material to adsorb and separate the mixture of the tetrahydropyrrole and the tetrahydrofuran.
The separation method adopts a non-porous self-adaptive ethoxy column [6] arene crystal material to purify the tetrahydropyrrole. The crystal material can effectively adsorb the tetrahydropyrrole with high selectivity from the mixture of the tetrahydropyrrole and the tetrahydrofuran, has low energy consumption, short balance time and simple operation, and solves the problems of high energy consumption, complex equipment, high operation risk coefficient and the like in the process of purifying the tetrahydropyrrole in industry.
Due to the difference in molecular structures of tetrahydropyrrole and tetrahydrofuran, the ethoxy column [6] arene crystal materials are able to form host-guest complexes with them in different stoichiometric ratios. Due to the difference of the stability of the main guest complex, the ethoxy column [6] arene crystal material can selectively adsorb the tetrahydropyrrole. The ethoxy column [6] arene crystal material is stable at the desorption temperature, can be reused after the desorption is completed, and the selectivity effect is not reduced.
The preparation method of the ethoxy column [6] arene crystal material comprises the following steps: adding terephthalyl ether into chloroform solvent, adding Lewis acid, reacting for 20-30 minutes at 25-30 ℃, quenching with sodium bicarbonate saturated solution after the reaction, washing with water, separating liquid, concentrating to obtain crude product, separating the crude product by column chromatography, recrystallizing, drying and activating to obtain the ethoxy column [6] arene crystal material.
The ethoxy column [6] arene crystal material after column chromatography separation and recrystallization can be activated by vacuum decompression drying and removing solvent molecules at 100-140 ℃ overnight. The activated ethoxy column [6] arene crystal material can be directly used for the adsorption separation of the tetrahydropyrrole and the tetrahydrofuran.
The separation method of the tetrahydropyrrole and the tetrahydrofuran specifically comprises the following steps: the ethoxy column [6] arene crystal material is placed in the mixed vapor atmosphere of the tetrahydropyrrole and the tetrahydrofuran, the temperature is 20-30 ℃, the adsorption time is determined according to the time for the tetrahydropyrrole to reach the adsorption saturation, and the adsorption time can be 2 hours, for example.
In the adsorption process, the cavity of the ethoxy column [6] arene crystal material is opened to contain gas molecules, so that the crystal form is changed. The tetrahydropyrrole in the mixed vapor forms a host-guest complex with the ethoxyl column [6] arene due to multiple weak interactions of hydrogen bond, CH-pi, pi-pi stacking, and the stoichiometric ratio of the host-guest complex is 1:1.
The volume ratio of the tetrahydropyrrole to the tetrahydrofuran in the mixed vapor is 1:99-99:1. The ethoxy column [6] arene crystal material is suitable for the adsorption separation of trace amount of tetrahydropyrrole and further desorption to obtain high-purity tetrahydropyrrole.
In the process of absorbing and separating the mixture of the tetrahydropyrrole and the tetrahydrofuran by the ethoxy column [6] arene crystal material, the surface of the ethoxy column [6] arene crystal material can absorb to form the mixture of the tetrahydropyrrole and the tetrahydrofuran. The mixture of the tetrahydropyrrole and the tetrahydrofuran adsorbed on the surface of the ethoxy column [6] arene crystal material can be removed by adopting a normal pressure heating or a reduced pressure heating mode.
Preferably, the temperature of the normal pressure heating or the reduced pressure heating is 30 to 40 ℃, and the conditions do not destroy the complexing force of the host and the guest, so that the host and the guest complex remain stably present, and the mixture adsorbed on the surface can be gradually removed. The heating time may be specific.
After the adsorption is finished, the adsorption complexing tetrahydropyrrole of the ethoxy column [6] arene crystal material can be desorbed by adopting a vacuum heating mode.
Preferably, the temperature of the vacuum heating is 100 to 140 ℃. The heating time may be specific.
The temperature condition damages the complexing force of the main body and the guest body, the adsorbed tetrahydropyrrole molecules are gradually released, the ethoxy column [6] arene crystal material is stable, and only the crystal form is changed in the desorption process. The ethoxy column [6] arene crystal material after the desorption is recovered to the state of being activated and completed initially, and can be continuously used for adsorbing and separating the tetrahydropyrrole and the tetrahydrofuran for the next cycle. The selectivity of the ethoxy column [6] arene crystal material to the pyrrolidine is not obviously changed after five adsorption and desorption cycles.
Compared with the prior art, the application has the main advantages that: the separation process is simple to operate, complex equipment is not needed, and the operation safety is good; the separation does not need rectification operation, so that energy sources are saved, and the production cost is reduced; the used crystal material has high stability, can be recycled, and the separation effect is not reduced.
Drawings
FIG. 1 is a powder X-ray diffraction (PXRD) diagram of the ethoxy column [6] arene crystal materials (EtP beta) of examples 1 and 2 and their adsorbed tetrahydropyrrole (Pyro) and Tetrahydrofuran (THF), respectively;
FIG. 2 is a graph showing the adsorption separation effect of the ethoxy column [6] arene crystal material of example 3 on a mixture of tetrahydropyrrole and tetrahydrofuran;
FIG. 3 is a graph showing the time adsorption profile of a binary mixture of pyrrolidine and tetrahydrofuran by adsorption separation from the ethoxy column [6] arene crystal material of example 3;
FIG. 4 is a graph showing the selectivity of adsorption separation effect of the ethoxy column [6] arene crystal material of example 5 when it is recycled.
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
Preparation of ethoxy column [6] arene crystal material: the ethoxy column [6] arene is prepared by using the p-benzene diethyl ether.
Paradiethyl ether (6.00 g,36 mmol) was added to 300mL of chloroform followed by BF 3 ·O(C 2 H 5 ) 2 (36-37 mmol), stirring the mixture at 25deg.C for 20-30 min, quenching with saturated sodium bicarbonate solution to finish the reaction, washing with deionized water twice, concentrating the organic phase under reduced pressure to obtain crude product, and purifying the crude product by flash column chromatography (volume ratio of petroleum ether/dichloromethane=1:4) to obtain ethoxy column [6]]Aromatic hydrocarbons (1.20 g, 15% yield) were white solid. Recrystallizing the white solid in dichloromethane, and placing in a vacuum oven at 140 ℃ overnight to obtain an activated ethoxyl column [6]]The aromatic hydrocarbon crystal material is white powder and is marked as EtP6.
The product characterization data prepared in this example are as follows:
EtP6, 1 H NMR(400MHz,CDCl 3 ,298K,ppm)δ6.69(s,12H),3.83(q,J=6.4Hz,24H),3.79(s,12H),1.28(t,J=6.4Hz,36H)。
the PXRD detection result is shown in figure 1, and the obtained ethoxy column [6] arene crystal material has good crystallinity.
Example 2
Adsorption of individual tetrahydropyrrole and tetrahydrofuran by ethoxy column [6] arene crystal material: two 20mL strain bottles were taken, 2mL of tetrahydropyrrole and tetrahydrofuran, designated as EtP6@pyro and EtP6@THF, were respectively added, 30mg of the ethoxy column [6] arene crystal material prepared in example 1 was respectively placed in two 5mL strain bottles, two open 5mL strain bottles were respectively placed in the two 20mL strain bottles, the 20mL strain bottles were sealed, and the strain bottles were left at room temperature of 25℃for 12 hours.
The product characterization data obtained in this example are as follows:
EtP6@Pyro, 1 H NMR(400MHz,CDCl3,298K,ppm)δ6.70(s,12H),3.82(dd,J=13.9,6.9Hz11136H),2.91(s,4H),1.72(s,4H),1.29(t,J=7.0111Hz,36H)。
EtP6@THF, 1 H NMR(400MHz,CDCl 3 ,298K,ppm)(400MHz,CDCl3111,298K,ppm)δ6.70(s,12H),3.82(dd,J=13.9,6.9Hz111,36H),3.76(s,8H),1.85(s,8H),1.29(t,J=7.0Hz,36H)。
1 h NMR results showed ethoxy column [6]]The arene crystal material can adsorb the tetrahydropyrrole in a stoichiometric ratio of 1:1; tetrahydrofuran can be adsorbed in a stoichiometric ratio of 1:2.
The PXRD detection result is shown in fig. 1, and relative to the PXRD spectrum of the initially activated ethoxyl column [6] arene crystal material, the PXRD spectrum of the ethoxyl column [6] arene crystal material after being placed in the vapor of the tetrahydropyrrole and the tetrahydrofuran for a period of time changes, which indicates that the unit cell parameters of the material change, namely, the tetrahydropyrrole and the tetrahydrofuran can be adsorbed into the ethoxyl column [6] arene crystal material; however, the PXRD spectra of the ethoxy column [6] arene crystal materials adsorbing the tetrahydropyrrole and the tetrahydrofuran are different, which shows that the materials show different microscopic crystal arrangement modes after adsorbing different components.
Example 3
The ratio of the ethoxyl column [6] arene crystal material to the volume is 1: adsorption of the mixture of tetrahydropyrrole and tetrahydrofuran of 1: two 20mL strain bottles, named A and B, are taken, 2mL of mixed solution prepared in advance according to the proportion is added into the A, 30mg of ethoxy column [6] arene crystal material prepared in example 1 is placed into a 5mL strain bottle, an open 5mL strain bottle is placed into the 20mL strain bottle A, the two 20mL strain bottles of A and B are sealed, the two strain bottles are placed at the normal temperature of 25 ℃ for 2 hours, and the concentration of each component in the two strain bottles of A and B is measured.
The product characterization data obtained in this example are as follows:
EtP6@(Pyro/THF), 1 H NMR(400MHz,CDCl 3 ,298K,ppm)δ6.70(s,12H),3.82(dd,J=13.9,6.9Hz,36H),3.76(s,0.2H),2.91(s,4H),1.85(s,0.2H),1.72(s,4H),1.29(t,J=7.0Hz,36H)。
at the position of 1 In the H NMR spectrum, the signal of hydrogen atom corresponding to the tetrahydropyrrole is strongWhile tetrahydrofuran has a weak signal for the hydrogen atom, indicating an ethoxy column [6]]The arene crystal material can selectively adsorb the tetrahydropyrrole.
The result of gas chromatography-mass spectrometry shows that, as shown in figure 2, the ethoxy column [6] arene crystal material can rapidly and selectively adsorb the tetrahydropyrrole, and finally the high-purity tetrahydropyrrole with the purity of more than 99.9% is obtained, so that the method has great industrial application prospect.
Determination of the optimal adsorption time: adsorption of ethoxy column [6] arene crystal material to a 1:1 by volume mixture of tetrahydropyrrole and tetrahydrofuran: 8 20mL strain bottles are taken, 1mL of tetrahydropyrrole and 1mL of tetrahydrofuran are respectively added, the materials are named EtP6 @6 (Pyro/THF 1-8), 30mg of ethoxy column [6] arene crystal materials prepared in example 1 are respectively placed in 5mL strain bottles, open 5mL strain bottles are placed in the 20mL strain bottles, the 20mL strain bottles are sealed and placed at the normal temperature of 25 ℃, one bottle is taken out every 15 minutes, and headspace gas chromatography test is carried out, so that a time-adsorption rate curve is obtained.
The results of the headspace gas chromatography are shown in fig. 3, and show that the ethoxy column [6] arene crystal material can selectively adsorb tetrahydropyrrole, the selectivity of which gradually increases from 98.1% to more than 99.9%, wherein the adsorption separation effect reaches the maximum value at 2 hours.
Example 4
Regeneration of ethoxy column [6] arene crystal material: 30mg of the ethoxy column [6] arene crystal material saturated with the adsorbed heterocyclic compound was heated in a vacuum oven at 100℃for 12 hours, designated EtP6-D.
The product characterization data obtained in this example are as follows:
EtP6-D, 1 H NMR(400MHz,CDCl 3 ,298K,ppm)δ6.69(s,12H),3.83(q,J=6.4Hz,24H),3.79(s,12H),1.28(t,J=6.4Hz,36H)。
at the position of 1 The signal of the hydrogen atom corresponding to the tetrahydropyrrole was found to have disappeared in the H NMR spectrum, indicating that the ethoxy column [6]]The aromatic hydrocarbon crystal material has completed desorption regeneration and has completely released the tetrahydropyrrole molecules.
Example 5
Ethoxy column [6] recycling of aromatic hydrocarbon crystal material: example 3 was repeated with 30mg of the regenerated ethoxycolumn [6] arene crystal material of example 4.
The results of headspace gas chromatography show that the ethoxy column [6] arene crystal material can selectively adsorb tetrahydropyrrole, and the selectivity is not significantly reduced in 5 cycles of adsorption experiments, as shown in fig. 4.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (9)
1. The application of the ethoxy column [6] arene crystal material in selectively adsorbing the tetrahydropyrrole is characterized in that the structural formula of the ethoxy column [6] arene crystal material is as follows:
2. the separation method of the tetrahydropyrrole and the tetrahydrofuran is characterized in that an ethoxy column [6] arene crystal material is utilized for adsorption separation of a mixture of the tetrahydropyrrole and the tetrahydrofuran, and the ethoxy column [6] arene crystal material has the following structural formula:
3. the method for separating pyrrolidine from tetrahydrofuran according to claim 2, wherein the method for preparing the ethoxy column [6] arene crystal material comprises the steps of: adding terephthalyl ether into chloroform solvent, adding Lewis acid, reacting for 20-30 minutes at 25-30 ℃, quenching with sodium bicarbonate saturated solution after the reaction, washing with water, separating liquid, concentrating to obtain crude product, separating the crude product by column chromatography, recrystallizing, drying and activating to obtain the ethoxy column [6] arene crystal material.
4. The method for separating the tetrahydropyrrole from the tetrahydrofuran according to claim 2, wherein the method for separating the tetrahydropyrrole from the tetrahydrofuran is specifically as follows: the ethoxy column [6] arene crystal material is placed in the mixed vapor atmosphere of the tetrahydropyrrole and the tetrahydrofuran, the temperature is 20-30 ℃, and the adsorption time is determined according to the time for the tetrahydropyrrole to reach the adsorption saturation.
5. The method for separating pyrrolidine from tetrahydrofuran according to claim 4, wherein the volume ratio of the pyrrolidine to the tetrahydrofuran in the mixed vapor is 1:99 to 99:1.
6. The method for separating the pyrrolidine and the tetrahydrofuran according to claim 2, wherein the mixture of the pyrrolidine and the tetrahydrofuran adsorbed on the surface of the crystalline material of the ethoxy column [6] arene is removed by heating under normal pressure or heating under reduced pressure.
7. The method for separating pyrrolidine from tetrahydrofuran according to claim 6, wherein the temperature of the normal pressure heating or the reduced pressure heating is 30 to 40 ℃.
8. The method for separating the tetrahydropyrrole and the tetrahydrofuran according to claim 2, wherein the adsorption-complexing tetrahydropyrrole of the aromatic hydrocarbon crystal material of the ethoxy column [6] is desorbed by adopting a vacuum heating mode.
9. The method for separating pyrrolidine from tetrahydrofuran according to claim 8, wherein the temperature of vacuum heating is 100 to 140 ℃.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009044007A2 (en) * | 2007-07-27 | 2009-04-09 | Sanofi-Aventis | 1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine-6-carboxamide and 2,3,4,5-tetrahydropyrrolo[1,2-a][1,4]-diazépine-7-carboxamide derivatives, preparation and therapeutic use thereof |
CN109206570A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application |
CN111362774A (en) * | 2020-03-03 | 2020-07-03 | 浙江大学 | Application of ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compound |
CN112142545A (en) * | 2020-09-29 | 2020-12-29 | 浙江大学 | Method for separating isopropyl benzene and alpha-methyl styrene |
-
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- 2022-01-13 CN CN202210035631.1A patent/CN114522668B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009044007A2 (en) * | 2007-07-27 | 2009-04-09 | Sanofi-Aventis | 1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine-6-carboxamide and 2,3,4,5-tetrahydropyrrolo[1,2-a][1,4]-diazépine-7-carboxamide derivatives, preparation and therapeutic use thereof |
CN109206570A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application |
CN111362774A (en) * | 2020-03-03 | 2020-07-03 | 浙江大学 | Application of ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compound |
CN112142545A (en) * | 2020-09-29 | 2020-12-29 | 浙江大学 | Method for separating isopropyl benzene and alpha-methyl styrene |
Non-Patent Citations (2)
Title |
---|
"Hydrogen adsorption on pillar[6]arene: A computational study";I.K. Petrushenko et al.;《Physica E: Low-dimensional Systems and Nanostructures》;第130卷;第 114719(1-7)页 * |
"柱芳烃纳客在吸附和分离中的应用";周玉娟等;《中国科学: 化学》;第49 卷;第832-843页 * |
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