CN113061088B - Asymmetric column [5] arene and preparation method and application thereof - Google Patents
Asymmetric column [5] arene and preparation method and application thereof Download PDFInfo
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- CN113061088B CN113061088B CN202110382716.2A CN202110382716A CN113061088B CN 113061088 B CN113061088 B CN 113061088B CN 202110382716 A CN202110382716 A CN 202110382716A CN 113061088 B CN113061088 B CN 113061088B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
- C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
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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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
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- 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 invention discloses an asymmetric column [5]]Aromatic hydrocarbon and a preparation method and application thereof, belonging to the technical field of high molecular compounds. The asymmetric column [5]]Aromatic hydrocarbon, its structural formula is shown as following formula:
asymmetric column (5) designed and synthesized by the invention]Aromatic hydrocarbon P1 is used as a novel non-porous self-adaptive crystal, has unique functional groups and a cavity structure, can be used for carrying out selective adsorption separation on dichloromethane in mixed gas of dichloromethane, trichloromethane and methyl iodide, and has the advantages of selectivity and reversibility.
Description
Technical Field
The invention belongs to the technical field of high molecular compounds, and in particular relates to an asymmetric column [5] arene and application thereof in selective adsorption and separation of mixed halogenated hydrocarbon.
Background
In recent years, organic materials based on supermolecular macrocyclic compound crystals have been rapidly developed and applied to the fields of biological medicine, molecular recognition and the like, wherein one class of macrocyclic compounds is seemingly nonporous materials, but has a cavity structure or lattice cavity available for guest molecules, and the materials can interact with a host guest generated by a guest through the special cavity structure so as to achieve the effect of adsorbing certain specific molecules, and are called as Nonporous Adaptive Crystals (NACs). Column aromatics, which are cyclic structures oligomerized by bridging between the 2, 5-positions of monomers with methylene groups and generally possess 5-10 repeating units, are also widely used as new generation macrocyclic host compounds for NACs materials. Compared with the traditional macrocyclic compound, the column arene has the characteristics of rigid structure, easy functionalization and the like, and can carry out host-guest complexation with more kinds of guest molecules, so that the organic material based on the column arene crystal can be used as an excellent NACs material. In the research process of the column arene, the synthesis of different functionalized column arene structures is the focus of many scholars, but asymmetric column arene has not been widely studied because of low yield, difficult separation of isomers and the like.
Most of the prior column aromatics applied to NACs materials have known symmetrical structures, such as methoxy column [5] aromatics or column [4] aromatics [1] quinones and derivatives thereof, and the like, and reports on asymmetric column aromatics are concentrated on the structures, so that the application research is less.
Disclosure of Invention
It is an object of the present invention to design and synthesize a new type of asymmetric column [5] arene.
It is another object of the present invention to provide the use of the novel asymmetric column [5] aromatics in the selective adsorption and separation of mixed halogenated hydrocarbons.
In order to achieve the above object, the present invention adopts the following technical scheme:
an asymmetric column [5] arene has a structural formula shown in the following formula:
the asymmetric column [5] arene is synthesized by adopting a route shown in the following formula:
the application of the asymmetric column [5] arene in the adsorption separation of halogenated alkane.
The haloalkane is dichloromethane.
The asymmetric column [5] arene P1 designed and synthesized by the invention has unique functional groups and a cavity structure as a novel non-porous adaptive crystal, can selectively adsorb and separate dichloromethane in mixed gas of dichloromethane, trichloromethane and methyl iodide, can separate adsorbed gas under specific conditions, and has the advantages of selectivity and reversibility.
The selective adsorption of the asymmetric column [5] arene P1 to the dichloromethane gas molecules is mainly due to the fact that the column arene P1 molecules can form a stable crystal structure after capturing dichloromethane, which can be seen through single crystal structure analysis of the figure I, and the generation of a new crystal structure after adsorption is proved through PXRD side surfaces.
Drawings
FIG. 1 shows the single crystal structure analysis of asymmetric column [5] arene P1 after adsorption of methylene chloride.
FIG. 2 shows nuclear magnetic resonance spectrum of an asymmetric column [5] arene P1 adsorbed on a sample, wherein (a) is methylene dichloride, (b) is chloroform, (c) is methyl iodide, and (d) is a mixed gas of the three.
FIG. 3 is a powder X-ray diffraction pattern of asymmetric column [5] arene P1 after adsorption of methylene chloride.
FIG. 4 is a gas chromatogram of the gas released after adsorption of dichloromethane by the asymmetric column [5] arene P1.
Detailed Description
The invention will now be described in further detail with reference to the drawings and specific examples, which should not be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention. The experimental procedures and reagents not shown in the formulation of the examples were all in accordance with the conventional conditions in the art.
Example 1
The synthetic route of the novel asymmetric column [5] arene P1 is as follows:
the preparation process comprises the following steps:
(1) Synthesis of monomer 2: in a 100mL round bottom flask, hydroquinone (2.2 g,0.02 mol) and 3-bromopropyne (2.4 g,0.02 mol) were dissolved in 50mL acetone, heated under magnetic stirring for 12h and the TCL was checked for progress. After the reaction was completed, the system was concentrated, and the crude product was separated by thin layer chromatography (PE: ea=50:1) to give monomer 1 as a brown oily liquid. Monomer 1 (3.0 g,0.02 mol) and methyl chloroacetate (4.3 g,0.04 mol) were weighed into a 100mL round bottom flask in 50mL acetone and heated under magnetic stirring for 12h under reflux, and TCL was checked for reaction progress. After the reaction was completed, the system was concentrated, and the crude product was washed 2-3 times with 30mL to give monomer 2 as a white solid in 56% yield.
(2) Synthesis of asymmetric column [5] arene P1: monomer 2 (2.2 g,0.01 mol) and trioxymethylene (1.7 g,0.02 mol) were dissolved in 50mL of methylene chloride in a 100mL round bottom flask, stirred at room temperature for 30min, then added with 1mL of boron trifluoride diethyl ether and stirred at room temperature for 4h, and TCL was used to detect the progress of the reaction. After the reaction, the system was concentrated and the crude product was chromatographed on thin layer chromatography (PE: DCM: ea=10:5:1), recrystallised from ethanol and filtered off with suction to give pale yellow solid P1.
P1.a pale yellow solid, 1%, 1 H NMR(400MHz,CDCl 3 )δ:6.91(s,5H,ArH),δ:6.88(s,5H,ArH),δ:4.59-4.58(d,10H,OCH 2 ),δ:4.53(s,10H,OCH 2 ),δ:3.83(s,10H,CH 2 ),δ:3.49(s,15H,OCH 3 ),δ:2.34-2.33(t,5H,CH).
example 2
Adsorption of halocarbon gas based on asymmetric column [5] arene P1 as non-porous adaptive crystal material
Four groups of 50mg asymmetric columns [5] arene P1 are weighed in a gas phase sample injection bottle, the four groups of samples are respectively placed in the atmosphere of dichloromethane, methyl iodide, chloroform and equal amount of mixed gas of the dichloromethane, the methyl iodide, the chloroform and the equal amount of mixed gas, and the four groups of samples are subjected to nuclear magnetic resonance hydrogen spectrum analysis, powder X-ray diffraction analysis and other characterization.
Through nuclear magnetic resonance hydrogen spectrum 1 H NMR), single crystal structure analysis, powder X-ray diffraction (P-XRD), and the like, on the synthesized asymmetric column [5]]The aromatic hydrocarbon is characterized.
Fig. 1 shows single crystal structure analysis of the asymmetric column [5] arene P1 after absorbing dichloromethane, and can show that dichloromethane molecules are absorbed in the cavity of the asymmetric column [5] arene P1 through host-guest interaction, which proves that the synthesized material can absorb and separate dichloromethane under certain conditions.
FIG. 2 shows the nuclear magnetic resonance spectrum of the asymmetric column [5] arene P1 after adsorption of four groups of samples, as follows: in the atmosphere of single dichloromethane (a) and trichloromethane (b), the asymmetric column [5] arene P1 can adsorb gas molecules, in the atmosphere of methyl iodide (c), the nuclear magnetic resonance hydrogen spectrum of the asymmetric column [5] arene P1 has no peak change, no adsorption to methyl iodide gas can be realized, and in the atmosphere of the mixed gas (d), the asymmetric column [5] arene P1 can realize selective adsorption of dichloromethane gas in three gases.
FIG. 3 shows powder X-ray diffraction analysis of asymmetric column [5] arene P1 after adsorption of methylene chloride, as follows: after adsorption of dichloromethane, the P-XRD peak of the asymmetric column [5] arene P1 is obviously changed compared with the intensity and the intensity before adsorption, which shows that the column arene P1 forms a new structure after adsorption.
FIG. 4 shows a gas chromatograph of the asymmetric column [5] arene P1 adsorbed methylene chloride followed by heating to release gas, as can be seen: after the adsorbed column aromatic hydrocarbon material is heated to 100 ℃, the adsorbed gas can be released from the cavity of the column aromatic hydrocarbon, and the released gas is subjected to gas chromatography analysis, so that the content of dichloromethane can reach more than 99%, the selective adsorption capacity is higher, and the recycling can be realized.
Example 3
Test of adsorption and separation effects of non-porous adaptive crystal material
The adsorption and separation effects of the prepared material on the mixed halogenated hydrocarbon are analyzed by a headspace gas chromatography, a sample after adsorption is sealed and heated in vacuum at 100 ℃ for 10 hours, and then the composition of the gas at the top of a gas-phase sample injection bottle is analyzed by the gas chromatography, wherein 99.1% of the gas adsorbed by the gas-phase sample injection bottle is found to be dichloromethane. And the material can release adsorbed gas after heating, so that recycling can be realized. Fig. 4 is a gas chromatogram of the released gas.
Claims (3)
1. An asymmetric column [5] arene has a structural formula shown in the following formula:
2. the asymmetric column [5] arene according to claim 1, synthesized using a route of the formula:
3. use of an asymmetric column [5] arene according to claim 1, wherein: in the mixed gas of dichloromethane, trichloromethane and methyl iodide, the asymmetric column [5] arene is subjected to selective adsorption separation on the dichloromethane.
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| CN114832857B (en) * | 2022-04-20 | 2023-09-19 | 南通大学 | Size selective catalyst based on column aromatic hydrocarbon and application thereof |
| CN115286524B (en) * | 2022-08-10 | 2023-09-01 | 浙江大学杭州国际科创中心 | Cyclobutylamine modified Shan Kunzhu [5] arene crystal material and preparation method and application thereof |
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