CN114522668A - 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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- CN114522668A CN114522668A CN202210035631.1A CN202210035631A CN114522668A CN 114522668 A CN114522668 A CN 114522668A CN 202210035631 A CN202210035631 A CN 202210035631A CN 114522668 A CN114522668 A CN 114522668A
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- crystal material
- pyrrolidine
- tetrahydrofuran
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000013078 crystal Substances 0.000 title claims abstract description 65
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 title claims abstract description 52
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 94
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000002178 crystalline material Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 3
- 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
- 238000001953 recrystallisation Methods 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
- 238000001994 activation Methods 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002360 preparation method Methods 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
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims 2
- 239000004258 Ethoxyquin Substances 0.000 claims 1
- 229940093500 ethoxyquin Drugs 0.000 claims 1
- 235000019285 ethoxyquin Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000003197 catalytic 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
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 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
- 230000000536 complexating effect Effects 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
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method 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
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- KOFIDSXHWGFEMO-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrolidine Chemical compound CC(C)CN1CCCC1 KOFIDSXHWGFEMO-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
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000009825 accumulation Methods 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
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 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
- 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
- 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
- 238000004817 gas chromatography Methods 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
- 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
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses an ethoxy column [6]]Application of aromatic hydrocarbon crystal material in selective adsorption of tetrahydropyrrole, ethoxy column [6]]The structural formula of the aromatic hydrocarbon crystal material is as follows:
the invention also discloses a tetrahydroMethod for separating pyrrole and tetrahydrofuran by using ethoxy column [6]]And adsorbing and separating the mixture of the tetrahydropyrrole and the tetrahydrofuran by using an aromatic hydrocarbon crystal material. 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, thereby saving energy and reducing production cost; the used crystal material has high stability, can be recycled, and the separation effect cannot be reduced.
Description
Technical Field
The invention relates to the field of adsorption separation, in particular to application of an ethoxy column [6] arene crystal material in selective adsorption of pyrrolidine.
Background
Tetrahydropyrrole is an intermediate for producing a series of medical products such as buflomedil Hydrochloride, Bepridil Hydrochloride, Acrivastine and the like. The literature reports mainly include: a catalytic hydrogenation method using pyrrole or dihydropyrrole as a raw material (Journal of the American Chemical Society,131(16), 5812-5822; 2009); succinimide or pyrrolidone as raw material into a ring method [ Chemistry & Industry (London, United Kingdom), (17), 547-8; 1990 ]; high-temperature high-pressure amination of 1, 4-butanediol to form a ring [ J.org.chem,1994,59(14),3998] and catalytic amination of tetrahydrofuran [ Journal of Catalysis,1974,35: 325-.
At present, industrial tetrahydropyrrole is mainly obtained by a tetrahydrofuran catalytic ammoniation method, which comprises catalytic ammoniation, rectification purification and molecular sieve drying. However, in the production of tetrahydropyrrole, due to limitations in conversion and molar yield, a part of the starting tetrahydrofuran and by-products including N-methyltetrahydropyrrole, N-N-butyltetrahydropyrrole, N-isobutyltetrahydropyrrole, etc. always remain. The presence of these by-products not only seriously affects the odor and acid-wash color of the tetrahydropyrrole, but also limits its further processing. Since tetrahydropyrrole (87.0 ℃) is close to tetrahydrofuran (67.0 ℃) and N-methyl tetrahydropyrrole (81.0 ℃), these impurities are difficult to remove, and the purity of tetrahydropyrrole is affected. Therefore, how to separate impurities such as pyrrolidine and tetrahydrofuran becomes a key link for purifying pyrrolidine.
Chinese patent publication No. CN 101948448A discloses a method for preparing and purifying pyrrolidine. The method comprises the steps of firstly, replacing the original filler in a rectifying tower with a ZSM-5 molecular sieve as an adsorbent, then enabling the produced crude product of the tetrahydropyrrole to enter a tower kettle of the rectifying tower in a liquid phase manner, carrying out normal-pressure continuous rectification, and receiving 86-87 ℃ fraction. The method can well remove most harmful impurities and improve the purity of the pyrrolidine.
However, the temperature required in the rectification process of the method is high, huge energy consumption is required, and the method is not beneficial to the development of green energy in China; and the maintenance cost of the rectification equipment is high, the production cost of an enterprise is improved, and the economic benefit of the enterprise is reduced.
In conclusion, finding a novel method which can effectively separate pyrrolidine and tetrahydrofuran and requires less energy consumption becomes the key of pyrrolidine purification in the industry at present.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides the application of the ethoxy column [6] arene crystal material in selective adsorption of the tetrahydropyrrole, the tetrahydropyrrole can be adsorbed at high selectivity 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 selective adsorption of pyrrolidine is characterized in that the structural formula of the ethoxy column [6] arene crystal material is as follows:
the invention also provides a method for separating the tetrahydropyrrole and the tetrahydrofuran, which is used for adsorbing and separating the mixture of the tetrahydropyrrole and the tetrahydrofuran by using an ethoxy column [6] aromatic hydrocarbon crystal material.
The separation method adopts a non-porous self-adaptive ethoxy column [6] arene crystal material to purify the pyrrolidine. The crystal material can effectively adsorb the pyrrolidine from the mixture of the pyrrolidine and tetrahydrofuran in high selectivity, has low energy consumption, short equilibrium time and simple operation, and solves the problems of high energy consumption, complex equipment, high operation risk coefficient and the like in the industrial pyrrolidine purification process.
Due to the difference of molecular structures of tetrahydropyrrole and tetrahydrofuran, the ethoxy column [6] arene crystal material can form a host-guest complex with different stoichiometric ratios with the tetrahydropyrrole and the tetrahydrofuran. Due to the difference of the stability of the host-guest complex, the ethoxy column [6] arene crystal material can selectively adsorb the pyrrolidine. The ethoxy column [6] arene crystal material is stable at the desorption temperature, can be repeatedly used after the desorption is completed, and the selectivity effect cannot be reduced.
The preparation method of the ethoxy column [6] arene crystal material comprises the following steps: adding p-phenyl diethyl ether into a trichloromethane solvent, adding Lewis acid, reacting for 20-30 minutes at 25-30 ℃, quenching with a saturated solution of sodium bicarbonate after the reaction is finished, washing with water, separating liquid, concentrating to obtain a crude product, and performing column chromatography separation, recrystallization, drying and activation on the crude product to obtain the ethoxy column [6] arene crystal material.
The ethyoxyl column [6] arene crystal material subjected to column chromatography separation and recrystallization can be activated by removing solvent molecules through vacuum reduced pressure drying and overnight mode at 100-140 ℃. The activated ethoxy column [6] arene crystal material can be directly used for adsorption separation of tetrahydropyrrole and tetrahydrofuran.
The method for separating the tetrahydropyrrole and the tetrahydrofuran specifically comprises the following steps: placing the ethoxy column [6] arene crystal material in a mixed steam atmosphere of pyrrolidine and tetrahydrofuran, wherein the temperature is 20-30 ℃, and the adsorption time is determined according to the time for the pyrrolidine to reach adsorption saturation, and can be 2 hours for example.
In the adsorption process, the cavity of the ethoxy column [6] arene crystal material is opened to accommodate gas molecules, so that the crystal form is changed. Because of multiple weak interactions of hydrogen bond, CH-pi and pi-pi accumulation, the pyrrolidine in the mixed vapor and the ethoxypillared [6] arene form a host-guest complex with the stoichiometric ratio of 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 adsorption separation of trace tetrahydropyrrole and further desorption to obtain high-purity tetrahydropyrrole.
In the process that the ethyoxyl column [6] arene crystal material adsorbs and separates the mixture of the tetrahydropyrrole and the tetrahydrofuran, the surface of the ethyoxyl column [6] arene crystal material can adsorb 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] aromatic hydrocarbon crystal material can be removed by adopting a normal pressure heating or reduced pressure heating mode.
Preferably, the temperature of the normal pressure heating or the reduced pressure heating is 30-40 ℃, and the complexing force of the host and the guest is not damaged under the condition, so that the host and guest complex still exist stably, and the mixture adsorbed on the surface can be removed gradually. The heating time may be specifically determined.
After adsorption, the vacuum heating mode can be adopted to desorb the tetrahydropyrrole adsorbed and complexed by the ethoxy column [6] arene crystal material.
Preferably, the temperature of the vacuum heating is 100-140 ℃. The heating time may be specifically determined.
The temperature condition destroys the complexing action of the host and the guest, the absorbed tetrahydropyrrole molecules can be gradually released, and the ethyoxyl column [6] arene crystal material is stable and only changes the crystal form in the desorption process. And the desorbed ethoxy column [6] arene crystal material is restored to the initial activated state and can be continuously used for adsorbing and separating pyrrolidine and tetrahydrofuran for the next cycle. The selectivity of the ethoxy column [6] arene crystal material to the pyrrolidine is not obviously changed after five times of adsorption and desorption cycles.
Compared with the prior art, the invention 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, thereby saving energy and reducing production cost; the used crystal material has high stability, can be recycled, and the separation effect cannot be reduced.
Drawings
FIG. 1 is a powder X-ray diffraction (PXRD) pattern of an ethoxypillared [6] arene crystalline material (EtP6 β) of example 1 and example 2 after adsorption of tetrahydropyrrole (Pyro) and Tetrahydrofuran (THF), respectively;
FIG. 2 is a graph showing the effect of the ethoxypillared [6] arene crystalline material of example 3 on the adsorptive separation of a mixture of pyrrolidine and tetrahydrofuran;
FIG. 3 is a gas chromatography characterization time adsorption graph of a binary mixture of tetrahydropyrrole and tetrahydrofuran adsorbed and separated by an ethoxy column [6] arene crystal material of example 3;
FIG. 4 is a graph showing selectivity of adsorption separation effect of the ethoxy column [6] arene crystal material of example 5 when it is recycled.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Preparing an ethoxy column [6] arene crystal material: preparing ethoxy column [6] arene by utilizing p-phenyl diethyl ether.
To 300mL of chloroform was added p-phenylethyther (6.00g, 36mmol), and BF was added3·O(C2H5)2(36-37 mmol), stirring the mixed solution at 25 ℃ for 20-30 minutes, quenching the mixed solution by using a saturated sodium bicarbonate solution to finish the reaction, washing the mixed solution twice by using deionized water, concentrating an organic phase under reduced pressure to obtain a crude product, and purifying the crude product by using flash column chromatography (the volume ratio of petroleum ether to dichloromethane is 1:4) to obtain the ethoxy column [6]]The aromatic hydrocarbon (1.20g, 15% yield) was a white solid. Recrystallizing the white solid in dichloromethane, and placing the white solid in a vacuum oven at 140 ℃ overnight to obtain the activated ethoxy column [6]]Aromatic hydrocarbon crystalline material, white powder, noted EtP 6.
The product prepared in this example has the following characterization data:
EtP6，1H NMR(400MHz,CDCl3，298K，ppm)δ6.69(s,12H),3.83(q,J＝6.4Hz,24H),3.79(s,12H),1.28(t,J＝6.4Hz,36H)。
PXRD detection results are shown in figure 1, and the obtained ethyoxyl column [6] arene crystal material has good crystallinity.
Example 2
Adsorption of ethoxy column [6] arene crystal material to individual tetrahydropyrrole and tetrahydrofuran: two 20mL strain bottles are taken, 2mL of tetrahydropyrrole and tetrahydrofuran, which are named as EtP6@ Pyro and EtP6@ THF, are respectively added, 30mg of the ethyoxyl column [6] arene crystal material prepared in example 1 is respectively placed in the two 5mL strain bottles, the two open 5mL strain bottles are respectively placed in the two 20mL strain bottles, the 20mL strain bottles are sealed, and the mixture is placed for 12 hours at the normal temperature of 25 ℃.
The product characterization data obtained in this example are as follows:
EtP6@Pyro,1H 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,1H NMR(400MHz,CDCl3,298K,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)。
1h NMR results showed ethoxy column [6]]The aromatic hydrocarbon crystal material can adsorb the pyrrolidine 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 compared to the PXRD pattern of the initially activated ethoxy pillared [6] arene crystal material, the PXRD pattern of the ethoxy pillared [6] arene crystal material after being placed in tetrahydropyrrole and tetrahydrofuran vapor for a period of time both show changes, which indicates that the unit cell parameters of the material change, i.e. both tetrahydropyrrole and tetrahydrofuran can be adsorbed into the ethoxy pillared [6] arene crystal material; but PXRD spectrogram of the ethyoxyl column [6] arene crystal material adsorbing the tetrahydropyrrole and the tetrahydrofuran is different, which shows that the material shows different microcosmic crystal arrangement modes after adsorbing different components.
Example 3
The volume ratio of the ethoxy column [6] arene crystal material is 1:1 adsorption of a mixture of tetrahydropyrrole and tetrahydrofuran: two 20mL strain bottles are taken and named as A and B respectively, 2mL mixed solution prepared in advance according to the proportion is added into the A, 30mg of the ethyoxyl column [6] arene crystal material prepared in the example 1 is placed into a 5mL strain bottle, the 5mL strain bottle with an opening is placed into the 20mL strain bottle A, the two 20mL strain bottles of the A and the B are sealed, the mixture is placed at the normal temperature of 25 ℃ for 2 hours, and the concentration of each component in the two strain bottles of the A and the B is measured.
The product characterization data obtained in this example are as follows:
EtP6@(Pyro/THF),1H NMR(400MHz,CDCl3,298K,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)。
in that1In the H NMR spectrum, the hydrogen atom signal corresponding to tetrahydropyrrole is very strong, while the hydrogen atom signal corresponding to tetrahydrofuran is very weak, which indicates that the ethoxy column [6]]The aromatic hydrocarbon crystal material can selectively adsorb the pyrrolidine.
The results of gas chromatography-mass spectrometry show that, as shown in fig. 2, the ethoxy column [6] arene crystal material can adsorb pyrrolidine selectively and very fast, and high-purity pyrrolidine with purity of more than 99.9% is obtained finally, so that the method has great industrial application prospects.
Determination of optimum adsorption time: adsorption of an ethoxy column [6] arene crystal material to a mixture of tetrahydropyrrole and tetrahydrofuran in a volume ratio of 1: and (2) taking 8 20mL strain bottles, respectively adding 1mL of tetrahydropyrrole and 1mL of tetrahydrofuran, and naming the bottles as EtP6@ (Pyro/THF 1-8), respectively taking 30mg of the ethoxy column [6] arene crystal material prepared in example 1, placing the material in the 5mL strain bottles, placing the 5mL open strain bottles in the 20mL strain bottles, sealing the 20mL strain bottles, placing the bottles at the normal temperature of 25 ℃, taking out one bottle every 15 minutes, and performing headspace gas chromatography to obtain a time-adsorption rate curve.
The result of the headspace gas chromatography is shown in fig. 3, and the result shows that the ethoxy column [6] arene crystal material can selectively adsorb the pyrrolidine, the selectivity of the material gradually increases from 98.1 percent to more than 99.9 percent, and the adsorption separation effect reaches the maximum value within 2 hours.
Example 4
Regeneration of an ethoxy column [6] arene crystal material: 30mg of ethoxy column [6] arene crystal material saturated with adsorbed heterocyclic compounds is heated in a vacuum oven at 100 ℃ for 12 hours and is marked as EtP 6-D.
The product characterization data obtained in this example are as follows:
EtP6-D,1H NMR(400MHz,CDCl3,298K,ppm)δ6.69(s,12H),3.83(q,J＝6.4Hz,24H),3.79(s,12H),1.28(t,J＝6.4Hz,36H)。
in that1The signal of the hydrogen atom corresponding to tetrahydropyrrole in the H NMR spectrum had disappeared, indicating that the ethoxy column [6]The aromatic hydrocarbon crystal material has completed desorption regeneration, and has completely released pyrrolidine molecule.
Example 5
Recycling of an ethoxy column [6] arene crystal material: example 3 was repeated with 30mg of the regenerated ethoxypillared [6] arene crystalline material of example 4.
The result of the headspace gas chromatography shows that, as shown in fig. 4, the ethoxy column [6] arene crystal material can selectively adsorb the pyrrolidine, and the selectivity of the material is not obviously reduced in a 5-cycle adsorption experiment.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. The application of the ethoxy column [6] arene crystal material in selective adsorption of pyrrolidine is characterized in that the structural formula of the ethoxy column [6] arene crystal material is as follows:
2. a method for separating pyrrolidine and tetrahydrofuran is characterized in that a mixture of pyrrolidine and tetrahydrofuran is adsorbed and separated by using an ethoxy column [6] aromatic hydrocarbon crystal material, wherein the structural formula of the ethoxy column [6] aromatic hydrocarbon crystal material is as follows:
3. the method for separating pyrrolidine and tetrahydrofuran according to claim 2, wherein the preparation method of the ethoxypillared [6] arene crystalline material comprises: adding p-phenyl diethyl ether into a trichloromethane solvent, adding Lewis acid, reacting for 20-30 minutes at 25-30 ℃, quenching with a saturated solution of sodium bicarbonate after the reaction is finished, washing with water, separating liquid, concentrating to obtain a crude product, and performing column chromatography separation, recrystallization, drying and activation on the crude product to obtain the ethoxy column [6] arene crystal material.
4. The method for separating pyrrolidine and tetrahydrofuran according to claim 2, wherein the method for separating pyrrolidine and tetrahydrofuran specifically comprises: placing the ethoxy column [6] arene crystal material in a mixed steam atmosphere of pyrrolidine and tetrahydrofuran, wherein the temperature is 20-30 ℃, and the adsorption time is determined according to the time for achieving adsorption saturation of the pyrrolidine.
5. The method according to claim 4, wherein the volume ratio of the tetrahydropyrrole to the tetrahydrofuran in the mixed vapor is 1:99 to 99: 1.
6. The method for separating pyrrolidine from tetrahydrofuran according to claim 2, wherein the mixture of pyrrolidine and tetrahydrofuran adsorbed on the surface of the ethoxypillared [6] aromatic hydrocarbon crystal material is removed by heating under normal pressure or under reduced pressure.
7. The method according to claim 6, wherein the temperature of the atmospheric heating or the reduced-pressure heating is 30 to 40 ℃.
8. The method for separating pyrrolidine and tetrahydrofuran according to claim 2, wherein the adsorption of complexed pyrrolidine on the ethoxyquin [6] arene crystal material is desorbed by vacuum heating.
9. The method according to claim 8, wherein the temperature of the vacuum heating is 100 to 140 ℃.
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