CN112608245A - Cationic water-soluble inclined column [6] arene and synthetic method thereof - Google Patents
Cationic water-soluble inclined column [6] arene and synthetic method thereof Download PDFInfo
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- C07C217/14—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring
- C07C217/18—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring being further substituted
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Abstract
The invention discloses a cationic water-soluble inclined column [6] arene and a synthesis method thereof, belonging to the technical field of organic chemical synthesis. The method comprises the following steps: firstly, carrying out three-step derivatization on 1, 4-bis (2, 5-dihydroxybenzyl) benzene to obtain an inclined column [6] aromatic hydrocarbon monomer 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene; then, chloroform is used as a solvent, ferric trichloride is used as a catalyst, 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene is polymerized, and bromoethoxy inclined column [6] arene is obtained with high yield; finally, the cation type water-soluble inclined column [6] arene is obtained through salt forming reaction. The method has the advantages that the monomer is modified and then cyclized, so that the influence of larger reaction steric hindrance caused by overcrowding of a group is avoided, the synthetic yield is higher, and the method is an efficient synthetic method of the cationic water-soluble inclined column [6] arene.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a cationic water-soluble inclined column [6] arene and a synthesis method thereof.
Background
Pillar arenes, as recognized fifth generation macrocyclic hosts, have gained widespread attention and have been studied extensively and intensively due to the abundant derivatization modalities and excellent host-guest properties. The Yang Enwei subject group (Desymmetrized leaving pillar 6 arene, Angew Chem Int Ed Engl J, 2018,57(31):9853-9858) in 2018 firstly reported a macrocyclic arene, namely an inclined column [6] arene, which has a structure very similar to a column arene, and because the inclined column [6] arene structure has two benzene rings without substituent groups, the steric hindrance of the two benzene rings during rotation is far smaller than that of other benzene rings with substituent groups. Therefore, the macrocyclic molecule not only has a cavity with the same size as that of the conventional column [6] arene, but also has certain adaptability due to the flexibility of two unsubstituted benzene rings, so that the cavity of the inclined column [6] arene can be finely adjusted to a certain degree according to the structure of a guest molecule when the guest molecule is complexed, and the macrocyclic molecule is combined with the guest molecule with the maximum strength. Due to the highly adaptive cavity and other excellent properties not inferior to those of column [6] arene, the inclined column [6] arene is widely applied to the fields of isomer separation, analyte monitoring, drug transportation and the like.
However, the defects in the united states are that the synthesis steps of the cationic water-soluble inclined column [6] arene in the prior art are more, and meanwhile, the synthesis route of ring formation before modification also leads to lower total synthesis yield (1.5%), which also becomes an important factor for limiting the development of extensive research on the cationic water-soluble inclined column [6] arene. Therefore, it is urgent to develop a highly efficient synthesis method of aromatic hydrocarbons with inclined column [6 ].
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a cationic water-soluble inclined column [6] arene and a synthesis method thereof.
In order to solve the problem of low yield of the aromatic hydrocarbon of the cationic water-soluble inclined column [6], the invention develops a new synthesis method, starts from the same starting material 1, 4-diethoxybenzene, and effectively avoids the problem that the steric hindrance is too large and the derivation is not facilitated due to the fact that the starting material is subjected to cyclization first and then modification in the prior art by a method of carrying out cyclization reaction after modifying the monomer in a plurality of steps, so that the cationic water-soluble inclined column [6] aromatic hydrocarbon is efficiently synthesized (the total yield is 13.4%), and the method is not reported at present, and all the related synthesized monomers are not reported and have good novelty.
One of the objects of the present invention is to provide a cationic water-soluble inclined column [6] arene.
The second purpose of the invention is to provide a method for synthesizing the cationic water-soluble inclined column [6] arene.
The purpose of the invention is realized by at least one of the following technical solutions.
The cation type water-soluble inclined column [6] arene provided by the invention has the following structural formula (5):
wherein R is more than one of bromine salt of trimethylamine, bromine salt of triethylamine and the like.
In the preparation method of the cation type water-soluble inclined column [6] arene, the chemical reaction equation is as follows:
wherein: r is bromine salt such as trimethylamine and triethylamine.
The invention provides a method for preparing cationic water-soluble inclined column [6] arene, which comprises the following steps:
(1) reacting 1, 4-bis (2, 5-dihydroxybenzyl) benzene with ethyl bromoacetate under an alkaline condition to obtain a monomer A;
(2) reducing the monomer A in the step (1) by using anhydrous tetrahydrofuran as a solvent through lithium aluminum hydride to obtain a monomer B;
(3) dissolving the monomer B obtained in the step (2) in an acetonitrile solvent, and obtaining a 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer through an Appeal reaction;
(4) using chloroform as a solvent and ferric trichloride as a catalyst, and polymerizing the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer obtained in the step (3) and paraformaldehyde to obtain bromoethoxy inclined column [6] arene;
(5) and (3) refluxing the bromoethoxy inclined column [6] arene obtained in the step (4) and amine substances (trimethylamine, triethylamine and the like) by using ethanol as a solvent to obtain the cationic water-soluble inclined column [6] arene.
The chemical equation of the reaction of the 1, 4-bis (2, 5-dihydroxybenzyl) benzene and ethyl bromoacetate under the alkaline condition in the step (1) is as follows:
further, the reaction of the 1, 4-bis (2, 5-dihydroxybenzyl) benzene and ethyl bromoacetate in the step (1) under an alkaline condition specifically comprises the following steps:
adding anhydrous acetonitrile, 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer and anhydrous potassium carbonate into a container under the atmosphere of nitrogen, stirring for reaction, then adding ethyl bromoacetate and potassium iodide serving as a catalyst, carrying out reflux reaction, cooling to room temperature, carrying out suction filtration to obtain filtrate, concentrating the filtrate, and carrying out column chromatography separation to obtain the monomer A.
Further, the molar ratio of the 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer to anhydrous potassium carbonate is 10: 1-30: 1; the molar volume ratio of the anhydrous potassium carbonate to the anhydrous acetonitrile is 1: 2-1: 5 mol/L; the stirring reaction time is 30-50 min; the molar ratio of the ethyl bromoacetate to the 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer is 5: 1-20: 1; the molar ratio of the potassium iodide to the anhydrous potassium carbonate is 1: 100-1: 200 of a carrier; the temperature of the reflux reaction is 80-90 ℃, and the time of the reflux reaction is 36-72 h; the structural formula of the monomer A is shown as follows:
preferably, during the reaction of the 1, 4-bis (2, 5-dihydroxybenzyl) benzene and the ethyl bromoacetate under alkaline conditions, the stirring reaction time is 40 min.
Preferably, the reaction of the 1, 4-bis (2, 5-dihydroxybenzyl) benzene and ethyl bromoacetate in the step (1) is carried out under an alkaline condition, and specifically comprises the following steps:
100mL of anhydrous acetonitrile is added into a 150mL two-neck flask, 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer and anhydrous potassium carbonate (10eq) are sequentially added under the atmosphere of nitrogen, stirred for forty minutes at room temperature, ethyl bromoacetate (10eq) and a catalytic amount of potassium iodide (0.05eq) are added, the mixture is refluxed until the reaction is completed, cooled to the room temperature, filtered, washed by a filter cake, concentrated in filtrate, and separated by column chromatography to obtain a monomer A.
The chemical equation of the monomer B obtained by reducing the monomer A with anhydrous tetrahydrofuran as a solvent through lithium aluminum hydride in the step (2) is as follows:
further, in the step (2), the monomer a is reduced by lithium aluminum hydride with anhydrous tetrahydrofuran as a solvent to obtain the monomer B, which specifically includes:
adding tetrahydrofuran and a monomer A into a container under the nitrogen atmosphere and in a stirring state, adding lithium aluminum hydride in an ice bath state, returning to normal temperature, stirring, performing reflux reaction, cooling to room temperature, adding a sodium hydroxide solution in the ice bath state, and quenching the reaction until no bubbles are generated in a reaction liquid to obtain a viscous substance; dissolving the viscous substance with tetrahydrofuran, performing suction filtration, taking filtrate, performing spin drying, washing the obtained solid, and drying to obtain a monomer B; the molar ratio of the monomer A to tetrahydrofuran is 1: 8-1: 10 mol/L; the molar ratio of the lithium aluminum hydride to the monomer A is 20: 1-30: 1; the stirring treatment time is 4-12 h; the temperature of the reflux reaction is 60-80 ℃, and the time of the reflux reaction is 3-6 h; the structural formula of the monomer B is shown as follows:
preferably, in the process of obtaining the monomer B by reducing the monomer A with anhydrous tetrahydrofuran as a solvent through lithium aluminum hydride, the stirring treatment time is 6 h.
Preferably, in the process of obtaining the monomer B by reducing the monomer A with anhydrous tetrahydrofuran as a solvent through lithium aluminum hydride, the reflux reaction time is 4 h.
Preferably, in the process of obtaining the monomer B by reducing the monomer A with anhydrous tetrahydrofuran as a solvent through lithium aluminum hydride, the specific steps are as follows:
adding 100mL of redistilled tetrahydrofuran into a 250mL two-port reaction bottle, stirring and adding a monomer A under the nitrogen atmosphere, carrying out ice bath to 0 ℃, slowly adding lithium aluminum hydride (20eq) in batches, recovering the room temperature after the addition, stirring for 6h, refluxing for 4h, cooling to the room temperature, and quenching by using a sodium hydroxide solution with the concentration of 1mol/L under the ice bath condition until no bubbles are generated in a reaction solution; dissolving the obtained viscous substance with tetrahydrofuran, carrying out suction filtration, washing a filter cake with enough tetrahydrofuran, washing the obtained solid with water after spin-drying the filtrate, and drying the product to obtain a monomer B.
Dissolving the monomer B in an anhydrous acetonitrile solvent in the step (3), and obtaining the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer by an Appeal reaction, wherein the chemical equation is as follows:
further, in the step (3), the monomer B is dissolved in an anhydrous acetonitrile solvent, and an Appeal reaction is performed to obtain a 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer, specifically including:
adding the monomer B into anhydrous acetonitrile, and then adding triphenylphosphine and carbon tetrabromide under an ice bath state to react to obtain a reaction solution; pouring the reaction liquid into ice water, filtering to obtain a filter cake, washing and drying to obtain the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer; the molar volume ratio of the monomer B to the anhydrous acetonitrile is 1: 75-1: 100 mol/mL; the molar ratio of the triphenylphosphine to the carbon tetrabromide is 1: 1-1: 1.5; the molar ratio of the monomer B to the triphenylphosphine is 1: 10-1: 15; the reaction time is 3-5 h; the structural formula of the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer is shown as follows:
preferably, in the process of dissolving the monomer B in an anhydrous acetonitrile solvent to obtain the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer through an Appeal reaction, the reaction time is 3 h.
Preferably, the process of dissolving the monomer B in an anhydrous acetonitrile solvent to obtain the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer through the Appeal reaction is as follows:
adding 100mL of anhydrous acetonitrile into a 250mL two-mouth reaction bottle, adding the monomer (2) under stirring, carrying out ice bath to 0 ℃, adding triphenylphosphine (10eq) and carbon tetrabromide (10eq), reacting for 3h, pouring the reaction solution into a large amount of ice water, carrying out suction filtration to obtain a white filter cake, washing the filter cake with a large amount of methanol, and drying the obtained filter cake to obtain the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer.
The chemical equation of the process of polymerizing 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer and paraformaldehyde by using chloroform as a solvent and ferric trichloride as a catalyst to obtain the bromoethoxy inclined column [6] arene is as follows:
further, in the step (4), chloroform is used as a solvent, ferric chloride is used as a catalyst, and 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer and paraformaldehyde are polymerized to obtain bromoethoxy inclined column [6] arene, which specifically comprises:
mixing 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer with paraformaldehyde, adding chloroform in the nitrogen atmosphere, stirring for reaction to obtain a reaction solution, adding ferric trichloride in the reaction solution for polymerization reaction, quenching the reaction solution with water, standing for layering, taking an organic phase, and separating by using a chromatographic column to obtain the bromoethoxy inclined column [6] arene.
Further, the molar ratio of the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer to paraformaldehyde is 1: 3-1: 4; the molar volume ratio of the paraformaldehyde to the chloroform is 1: 250-1: 300 mol/L; the stirring reaction time is 0.3-0.5 h; the molar ratio of the ferric trichloride to the paraformaldehyde is 1: 15-1: 20; the polymerization reaction time is 0.5-3 h; the structural formula of the bromoethoxy inclined column [6] arene is shown as follows:
preferably, in the process of obtaining the bromoethoxy inclined column [6] arene by polymerizing 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer and paraformaldehyde by using chloroform as a solvent and ferric trichloride as a catalyst, the stirring reaction time is 0.5 h.
Preferably, in the process of obtaining the bromoethoxy inclined column [6] arene by polymerizing 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer and paraformaldehyde by using chloroform as a solvent and ferric trichloride as a catalyst, the polymerization reaction time is 40min, and the reaction can be monitored by using TLC platelets.
Preferably, the process of obtaining the bromoethoxy inclined column [6] arene by polymerizing 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer and paraformaldehyde with chloroform as a solvent and ferric chloride as a catalyst comprises the following steps:
adding bromoethoxy inclined column [6] arene and paraformaldehyde (3eq) into a 250mL two-mouth bottle, pumping nitrogen gas for solid, adding 150mL chloroform under nitrogen gas atmosphere, stirring reaction liquid for 0.5h, adding ferric trichloride (0.2eq) under nitrogen gas atmosphere, monitoring reaction by TLC platelet, basically disappearing raw material after about 40min, concentrating the product point, quenching the reaction by 200mL water, extracting by using a separating funnel to obtain an organic phase, spin-drying, and separating by using a chromatographic column to obtain the bromoethoxy inclined column [6] arene.
And (5) refluxing the bromoethoxy inclined column [6] arene and the amine by using ethanol as a solvent to obtain the cationic water-soluble inclined column [6] arene, wherein the chemical equation of the process is as follows:
further, the step (5) of refluxing the bromoethoxy inclined column [6] arene and the amine with ethanol as a solvent to obtain the cationic water-soluble inclined column [6] arene specifically comprises:
dissolving the bromoethoxy inclined column [6] arene in absolute ethyl alcohol, adding an amine solution under the atmosphere of nitrogen, then carrying out reflux reaction, cooling to room temperature to obtain a reaction solution, spin-drying the reaction solution, dissolving the obtained solid in water, carrying out suction filtration, taking a filtrate, and drying the filtrate to obtain the cationic water-soluble inclined column [6] arene.
Further, the concentration of the amine solution is 1-1.5 mol/L; the amine is more than one of trimethylamine and triethylamine; the molar ratio of the solute of the amine solution to the bromoethoxy inclined column [6] arene is 80: 1-100: 1; the temperature of the reflux reaction is 80-100 ℃, and the time of the reflux reaction is 24-36 h.
Preferably, in the process of refluxing bromoethoxy inclined column [6] arene and amine by using ethanol as a solvent to obtain the cationic water-soluble inclined column [6] arene, the reflux reaction time is 24 hours.
Preferably, in the process of refluxing the bromoethoxy inclined column [6] arene and the amine by using ethanol as a solvent to obtain the cationic water-soluble inclined column [6] arene, the molar ratio of the solute of the amine solution to the bromoethoxy inclined column [6] arene is 90: 1.
preferably, the process of refluxing the bromoethoxy inclined column [6] arene and the amine with ethanol as a solvent to obtain the cationic water-soluble inclined column [6] arene comprises the following steps:
dissolving bromoethoxy inclined column [6] arene in 50mL of absolute ethyl alcohol in a 100mL two-mouth reaction bottle, pumping nitrogen, adding amines (trimethylamine, triethylamine and the like) (wherein the amount of the amine is 80 times of that of the bromoethoxy inclined column [6] arene), refluxing for 24h under a sealed condition, cooling to room temperature, spin-drying reaction liquid, dissolving obtained solid with water, performing suction filtration, spin-drying filtrate, and drying to obtain cationic water-soluble inclined column [6] arene (water-soluble quaternary ammonium salt inclined column [6] arene).
Compared with the prior art, the invention has the following advantages and beneficial effects:
in the preparation method provided by the invention, the synthetic route of firstly modifying and then cyclizing is very efficient, energy is saved, and the ferric trichloride catalyst used in the cyclization reaction is cheap and easy to obtain, has no volatile toxicity, and is green and environment-friendly. The high-efficiency synthesis line is beneficial to popularization of wide application of the aromatic hydrocarbon of the inclined column [6 ].
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the monomer (1) in example 1.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the monomer (2) in example 1.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the monomer (3) in example 1.
FIG. 4 is a nuclear magnetic hydrogen spectrum of bromoethoxy-tilted column [6] arene (4) in example 1.
FIG. 5 is a nuclear magnetic hydrogen spectrum of the water-soluble quaternary ammonium salt inclined column [6] arene (5) in example 1.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
a. Synthesis of monomer (1): in a 150mL two-necked flask, 100mL of anhydrous acetonitrile was added, 4g (12.4mmol) of 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer and 17.2g of anhydrous potassium carbonate (124.2mmol) were sequentially added under a nitrogen atmosphere, stirred at room temperature for forty minutes, 15.2mL of ethyl bromoacetate (124.2mmol) and 245mg of a catalytic amount of potassium iodide (1.48mmol) were added, refluxed until the reaction was completed, cooled to room temperature, suction-filtered and the filter cake washed, the filtrate was concentrated, and separated by column chromatography to obtain monomer (1). 6.6g of the product was prepared in 80% yield, and the nuclear magnetic hydrogen spectrum of the monomer (1) is shown in FIG. 1. Nuclear magnetic hydrogen spectrum data:1H NMR(400MHz,CDCl3):δ7.16(d,J＝3.5Hz,4H),6.73(d,J＝5.8Hz,2H),6.71–6.57(m,4H),4.54(dd,J＝11.6,3.6Hz,8H),4.35–4.09(m,8H),3.99(d,J＝3.7Hz,4H),1.29(t,J＝6.8Hz,12H)。
b. synthesis of monomer (2): adding 100mL of redistilled tetrahydrofuran into a 250mL two-port reaction bottle, stirring and adding 4.0g (6mmol) of monomer (1) under the nitrogen atmosphere, carrying out ice bath to 0 ℃, adding 4.6g of lithium aluminum hydride (120mmol) in batches, recovering the room temperature after the addition, stirring for 6h, refluxing for 4h, cooling to the room temperature, and then quenching by using a sodium hydroxide solution with the concentration of 1mol/L under the ice bath condition until no bubbles are generated in the reaction solution. Dissolving the obtained viscous substance with tetrahydrofuran, performing suction filtration, washing a filter cake with enough tetrahydrofuran, washing the obtained solid with water after spin-drying the filtrate, and drying the product to obtain the monomer (2). Preparation of 2.7g of product in 89% yield of monomer (2)1The H NMR spectrum is shown in FIG. 2. Nuclear magnetic hydrogen spectrum data:1H NMR(400MHz,DMSO-d6):δ7.15(s,4H),6.86(d,J＝8.6Hz,2H),6.70(d,J＝12.8Hz,4H),4.78(q,J＝5.6Hz,4H),4.06–3.77(m,12H),3.68(dt,J＝19.7,5.1Hz,8H)。
c. synthesis of monomer (3): adding 100mL of anhydrous acetonitrile into a 250mL two-mouth reaction bottle, adding 1g (2mol) of monomer (2) under stirring, carrying out ice bath to 0 ℃, adding 5.3g of triphenylphosphine (20mmol) and 6.64g of carbon tetrabromide (20mmol), pouring the reaction liquid into 3L of ice water after reacting for 3h, carrying out suction filtration to obtain a white filter cake, washing the filter cake with a large amount of methanol, and drying the obtained filter cake to obtain the 1, 4-bis (2, 5-dibromo ethoxy benzyl) compound) A benzene monomer (3). Preparation of 0.8g of product, 55% yield, monomer (3)1The H NMR spectrum is shown in FIG. 3. Nuclear magnetic hydrogen spectrum data:1H NMR(400MHz,CDCl3):δ7.15(d,J＝3.9Hz,4H),6.78(d,J＝8.6Hz,2H),6.72(d,J＝9.3Hz,4H),4.22(t,J＝6.1Hz,8H),3.95(s,4H),3.59(dt,J＝12.1,6.3Hz,8H)。
d. synthesis of monomer (4): adding 690mg (1mmol) of monomer (3) and 90mg of paraformaldehyde (3mmol) into a 250mL two-mouth bottle, pumping nitrogen gas for solid, adding 150mL of chloroform under the nitrogen gas atmosphere, stirring the reaction solution for 0.5h, adding 33mg of ferric trichloride (0.2mmol) under the nitrogen gas atmosphere, monitoring the reaction by TLC platelet, basically eliminating the raw material after 40min, concentrating the product point to the maximum, quenching the reaction by 200mL of deionized water, obtaining an organic phase by using a separating funnel, spin-drying, and separating by using a chromatographic column to obtain a bromoethoxy inclined column [6]]An aromatic hydrocarbon (4). Preparation of 106mg of product in 35% yield using bromoethoxy inclined column [6]]Of aromatic hydrocarbons (4)1The H NMR spectrum is shown in FIG. 4. Nuclear magnetic hydrogen spectrum data:1H NMR(400MHz,CDCl3):δ7.04(s,8H),6.86(s,4H),6.63(s,4H),4.21(d,J＝6.8Hz,8H),4.13(d,J＝7.1Hz,8H),3.91(d,J＝11.4Hz,12H),3.62(d,J＝7.0Hz,8H),3.44(d,J＝7.1Hz,8H)。
e. synthesis of monomer (5): 380mg (0.25) bromoethoxy inclined column [6] was dissolved in 50mL absolute ethanol in a 100mL two-necked reaction flask]Aromatic hydrocarbon (4), pumping nitrogen, adding 4mL trimethylamine ethanol solution (20mmol), refluxing for 24h under sealed condition, cooling to room temperature, spin-drying reaction liquid, dissolving obtained solid with water, suction-filtering, spin-drying filtrate, and drying to obtain water-soluble quaternary ammonium salt inclined column [6]]An aromatic hydrocarbon (5). 489mg of product was prepared in 98% yield using a water-soluble quaternary ammonium salt inclined column [6]]Of aromatic hydrocarbons (5)1The H NMR spectrum is shown in FIG. 5. Nuclear magnetic hydrogen spectrum data:1H NMR(400MHz,D2δ 7.15(s,8H),7.02(s,4H),6.75(s,4H),4.48(s,8H),4.30(d, J ═ 6.1Hz,8H),3.89(d, J ═ 16.2Hz,12H),3.72(d, J ═ 5.5Hz,8H),3.53(d, J ═ 5.8Hz,8H),3.10(s,36H),2.87(s, 36H). (R is a bromine salt of trimethylamine).
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A cationic water-soluble tilted column [6] arene having the following structural formula:
wherein R is more than one of bromine salt of trimethylamine and bromine salt of triethylamine.
2. A method of preparing the cationic water-soluble inclined column [6] arene according to claim 1, wherein a chemical equation is as follows:
wherein R is more than one of bromine salt of trimethylamine and bromine salt of triethylamine.
3. The method of claim 2, comprising the steps of:
(1) reacting 1, 4-bis (2, 5-dihydroxybenzyl) benzene with ethyl bromoacetate under an alkaline condition to obtain a monomer A;
(2) reducing the monomer A in the step (1) by using anhydrous tetrahydrofuran as a solvent through lithium aluminum hydride to obtain a monomer B;
(3) dissolving the monomer B obtained in the step (2) in an acetonitrile solvent, and obtaining a 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer through an Appeal reaction;
(4) using chloroform as a solvent and ferric trichloride as a catalyst, and polymerizing the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer obtained in the step (3) and paraformaldehyde to obtain bromoethoxy inclined column [6] arene;
(5) and (3) refluxing the bromoethoxy inclined column [6] arene and the amine substance obtained in the step (4) by using ethanol as a solvent to obtain the cationic water-soluble inclined column [6] arene.
4. The method for preparing a cationic water-soluble inclined column [6] arene according to the claim 3, wherein the 1, 4-bis (2, 5-dihydroxybenzyl) benzene and ethyl bromoacetate in the step (1) are reacted under alkaline conditions, and the method specifically comprises the following steps:
adding anhydrous acetonitrile, 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer and anhydrous potassium carbonate into a container under the atmosphere of nitrogen, stirring for reaction, then adding ethyl bromoacetate and potassium iodide serving as a catalyst, carrying out reflux reaction, cooling to room temperature, carrying out suction filtration to obtain filtrate, concentrating the filtrate, and carrying out column chromatography separation to obtain the monomer A.
5. The preparation method of the cationic water-soluble inclined column [6] arene according to claim 4, wherein the molar ratio of the 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer to the anhydrous potassium carbonate is 10: 1-30: 1; the molar volume ratio of the anhydrous potassium carbonate to the anhydrous acetonitrile is 1: 2-1: 5 mol/L; the stirring reaction time is 30-50 min; the molar ratio of the ethyl bromoacetate to the 1, 4-bis (2, 5-dihydroxybenzyl) benzene monomer is 5: 1-20: 1; the molar ratio of the potassium iodide to the anhydrous potassium carbonate is 1: 100-1: 200 of a carrier; the temperature of the reflux reaction is 80-90 ℃, and the time of the reflux reaction is 36-72 h; the structural formula of the monomer A is shown as follows:
6. the method for preparing cationic water-soluble inclined column [6] arene according to the claim 3, wherein the step (2) is to obtain the monomer B by reducing the monomer A with anhydrous tetrahydrofuran as a solvent through lithium aluminum hydride, and specifically comprises the following steps:
adding tetrahydrofuran and a monomer A into a container under the nitrogen atmosphere and in a stirring state, adding lithium aluminum hydride in an ice bath state, returning to normal temperature, stirring, performing reflux reaction, cooling to room temperature, adding a sodium hydroxide solution in the ice bath state, and quenching the reaction until no bubbles are generated in a reaction liquid to obtain a viscous substance; dissolving the viscous substance with tetrahydrofuran, performing suction filtration, taking filtrate, performing spin drying, washing the obtained solid, and drying to obtain a monomer B; the molar ratio of the monomer A to tetrahydrofuran is 1: 8-1: 10 mol/L; the molar ratio of the lithium aluminum hydride to the monomer A is 20: 1-50: 1; the stirring treatment time is 4-12 h; the temperature of the reflux reaction is 60-80 ℃, and the time of the reflux reaction is 3-6 h; the structural formula of the monomer B is shown as follows:
7. the method for preparing the cationic water-soluble inclined column [6] arene according to the claim 6, wherein the monomer B is dissolved in an anhydrous acetonitrile solvent in the step (3) and is subjected to an Appeal reaction to obtain a 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer, and the method specifically comprises the following steps:
adding the monomer B into anhydrous acetonitrile, and then adding triphenylphosphine and carbon tetrabromide under an ice bath state to react to obtain a reaction solution; pouring the reaction liquid into ice water, filtering to obtain a filter cake, washing and drying to obtain the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer; the molar volume ratio of the monomer B to the anhydrous acetonitrile is 1: 75-1: 100 mol/mL; the molar ratio of the triphenylphosphine to the carbon tetrabromide is 1: 1-1: 1.5; the molar ratio of the monomer B to the triphenylphosphine is 1: 10-1: 15; the reaction time is 3-5 h; the structural formula of the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer is shown as follows:
8. the method for preparing the cationic water-soluble inclined column [6] arene according to the claim 3, wherein the bromoethoxy inclined column [6] arene is obtained by polymerizing 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer and paraformaldehyde by using chloroform as a solvent and ferric trichloride as a catalyst in the step (4), and specifically comprises the following steps:
mixing 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer with paraformaldehyde, adding chloroform in the nitrogen atmosphere, stirring for reaction to obtain a reaction solution, adding ferric trichloride in the reaction solution for polymerization reaction, quenching the reaction solution with water, standing for layering, taking an organic phase, and separating by using a chromatographic column to obtain the bromoethoxy inclined column [6] arene.
9. The method for preparing cationic water-soluble inclined column [6] arene according to claim 8, wherein the molar ratio of the 1, 4-bis (2, 5-dibromoethoxybenzyl) benzene monomer to paraformaldehyde is 1: 3-1: 4; the molar volume ratio of the paraformaldehyde to the chloroform is 1: 250-1: 300 mol/L; the stirring reaction time is 0.3-0.5 h; the molar ratio of the ferric trichloride to the paraformaldehyde is 1: 15-1: 20; the polymerization reaction time is 0.5-3 h; the structural formula of the bromoethoxy inclined column [6] arene is shown as follows:
10. the method for preparing the cationic water-soluble inclined column [6] arene according to the claim 3, wherein the ethanol is used as a solvent in the step (5), and the bromoethoxy inclined column [6] arene and the amine are refluxed to obtain the cationic water-soluble inclined column [6] arene, and the method specifically comprises the following steps:
dissolving the bromoethoxy inclined column [6] arene in absolute ethyl alcohol, adding an amine solution under the atmosphere of nitrogen, then carrying out reflux reaction, cooling to room temperature to obtain a reaction solution, spin-drying the reaction solution, dissolving the obtained solid with water, carrying out suction filtration, taking a filtrate, and drying the filtrate to obtain the cationic water-soluble inclined column [6] arene; the concentration of the amine solution is 1-1.5 mol/L; the amine is more than one of trimethylamine and triethylamine; the molar ratio of the solute of the amine solution to the bromoethoxy inclined column [6] arene is 80: 1-100: 1; the temperature of the reflux reaction is 80-100 ℃, and the time of the reflux reaction is 24-36 h.
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