CN113461701B - Calixarene-derivatized supramolecular macrocyclic host compound, preparation method and application thereof - Google Patents
Calixarene-derivatized supramolecular macrocyclic host compound, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a calixarene-derived supermolecule macrocyclic host compound, a preparation method and application thereof. The preparation method has the advantages of simple route and process, easily obtained raw materials, mild reaction conditions, high yield and good repeatability. The supermolecule cup compound disclosed by the invention has better water solubility, simultaneously provides a hydrophobic cavity capable of accommodating guest molecules, can selectively identify hydrophilic small molecules in water, including water pollutant 1, 4-dioxane, and has a potential prospect of being applied to environmental pollution detection, and fluorescence can be greatly changed after the 1, 4-dioxane is identified.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to a water-soluble pyridyl supermolecule cup, a preparation method and application thereof.
Background
Calixarenes are macrocyclic oligomers formed by the attachment of phenolic monomers via methylene groups in the ortho position to the phenolic hydroxyl group, and are structurally characterized as greek eriodictyon (calixcarater) and are referred to as calixarenes, the nomenclature of which is commonly referred to as calix [ n ] arene, where n represents the number of phenolic monomers forming the macrocycle (typically n =4,6,8), most commonly calix [4] arene and calix [6] arene.
In calixarene molecules, the upper edge is composed of para-substituent groups of benzene rings, the lower edge is generally composed of regularly arranged phenolic hydroxyl groups, the calixarene molecules have hydrophilicity, and the middle part is a hydrophobic electron-rich cavity composed of benzene rings, and compared with the first two generations of supermolecule main bodies, the calixarene molecules mainly have the following advantages:
1. the calixarene is convenient to synthesize, the raw materials are cheap and easy to obtain, and the research is convenient to develop;
2. has larger molecular weight, thus having high melting point, good chemical stability and lower toxicity;
3. easy derivatization, and the structure of the derivative determines that a substituent group at the para position of the upper edge benzene ring, phenolic hydroxyl at the lower edge and methylene among the benzene rings can be selectively modified, so that the physicochemical properties of the derivative, such as the solubility, the cavity size and the like, can be adjusted;
4. the hydrophobic cavity can be adjusted according to different guest molecules, and can complex various types of small molecule compounds;
5. the conformation is rich, various conformations exist, and the required conformation can be fixed by chemical modification and adjustment of conditions such as temperature, pH and the like.
The cavity of the supermolecule cup can adapt to more types of guest molecules, so that the synthesis of the water-soluble supermolecule cup is gradually concerned by researchers, and the construction of the cavity of the supermolecule cup is often accompanied with pi-pi accumulation, thereby leading to poor water solubility of a host molecule.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a calixarene-derivatized supramolecular macrocyclic host compound, a preparation method and application thereof. According to the preparation method of the supermolecule with good water solubility, the pyridine group is introduced to the upper edge of the water-soluble supermolecule cup, so that the depth of a cavity is increased, the in-and-out exchange of an object is slowed down, and the identification of hydrophilic micromolecules is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a calixarene-derivatized supramolecular macrocyclic host compound having at least four aromatic structures, capable of dissolving in water, having a hydrophobic cavity structure capable of accommodating a guest molecule, and also capable of selectively recognizing a hydrophilic small molecule in water, having a structure of at least one of the following supramolecular cup 1 and supramolecular cup 2:
the structural formula of the molecular cup 1 is as follows:
the structural formula of the molecular cup 2 is as follows:
preferably, when the supramolecular macrocyclic host compound derived from the calixarene disclosed by the invention has a structure of a molecular cup 1, the compound has a deep cavity, the main part of the cavity is a benzimidazole group, the upper edge of the main part is connected with a pyridine group with a nitrogen atom at the No. 4 position, the lower edge of the main part is a sodium carboxylate, the main part and the guest molecule form a vase conformation in water, and the guest molecule is wrapped in the cavity of the supramolecular cup.
Preferably, when the calixarene-derivatized supramolecular macrocyclic host compound has a structure of a molecular cup 2, the compound has a deep cavity, the main part of the cavity is a benzimidazole group, the upper edge of the main part is connected with a pyridine group with a nitrogen atom at the 3-position, the lower edge of the main part is a sodium carboxylate, the compound and a guest molecule form a vase conformation in water, and the guest molecule is wrapped in the cavity of the supramolecular cup.
The invention relates to a preparation method of a calixarene-derived supermolecule host compound, which takes resorcinol or derivatives thereof as initial reaction raw materials to prepare a water-soluble pyridyl supermolecule cup compound, introduces sodium carboxylate at the lower edge through oxidation reaction and hydrolysis reaction to achieve integral water solubility, introduces different pyridine groups at the upper edge through condensation with diamine to ensure that the middle part is a benzimidazole group, and the addition of pyridine at the upper edge reduces the caliber of a cavity to slow down object exchange.
Preferably, the preparation method of the calixarene-derivatized supramolecular macrocyclic host compound of the invention comprises the following synthetic steps:
a. using resorcinol or its derivative as raw material, adding Jones reagent into acetone solution of the raw material at 0 deg.C or higher, heating the reaction mixture to room temperature and stirring for at least 10 hr; the reaction was quenched by addition of 2-isopropanol and filtered; concentrating the filtrate by using a rotary evaporator to obtain a solid, thoroughly washing the solid with acetone and methanol respectively for at least 3 times, and then drying;
b. b, taking the product prepared in the step a and tin dichloride dihydrate as reactants, adding the product prepared in the step a into a round-bottom flask cooled in an ice bath, and suspending the product in ethanol pre-cooled to be not higher than 0 ℃ for stirring; slowly adding tin dichloride dihydrate and concentrated hydrochloric acid with the mass fraction not lower than 20% into the suspension, and replacing nitrogen for at least 3 times; then immersing the round bottom flask in an oil bath preheated to a temperature of not less than 110 ℃ and vigorously heated under reflux for at least 4 hours; cooling the reaction mixture to room temperature, filtering, washing the obtained solid with hydrochloric acid solution with the concentration of not higher than 3mol/L at the temperature of not higher than 0 ℃ for at least 3 times, then washing with acetonitrile at the temperature of not higher than 0 ℃ for at least 5 times, finally washing with diethyl ether for at least 5 times, and then drying;
c. dissolving the product prepared in the step b and 2- (4-pyridylmethylene) malononitrile as reactants with methanol, and adding 25-28% by mass of aqueous ammonia to obtain a white precipitate, then removing the solvent using a rotary evaporator, adding methanol to the flask while adding 2- (4-pyridylmethylene) malononitrile under nitrogen and vigorously stirring at a temperature of not higher than 80 ℃ for at least 15 hours, then filtering to obtain a solid, washing the solid with methanol at least 3 times, water at least 2 times, dichloromethane at least 1 time, collecting the solid, and drying under vacuum;
d. adding the product prepared in the step c and sodium hydroxide as reactants into another round-bottom flask, adding a mixed solvent of ethanol and tetrahydrofuran, and then adding an aqueous solution of sodium hydroxide at a temperature of not higher than 0 ℃; then the reaction mixture is transferred to the temperature of not lower than 40 ℃ and stirred for at least 10 hours; the resulting solid was then filtered and washed with ethanol at least 3 times; suspending the recovered solid in acetone, then stirring vigorously and heating under reflux for at least 1 hour, cooling the suspension to room temperature, filtering, washing with acetone, and drying under vacuum to obtain white solid supramolecular cup 1;
e. dissolving the product prepared in the step b and 2- (3-pyridylmethylene) malononitrile as reactants with methanol, adding 25-28% by mass of aqueous ammonia to obtain a white precipitate, removing the solvent using a rotary evaporator, adding methanol to the flask while adding 2- (3-pyridylmethylene) malononitrile under nitrogen and vigorously stirring at a temperature of not higher than 80 ℃ for at least 15 hours, filtering to obtain a solid, washing the solid with methanol at least 3 times, washing acetonitrile at least 2 times, collecting the solid, and drying under vacuum;
f. adding the product prepared in the step e and sodium hydroxide into the other round-bottom flask as reactants, adding a mixed solvent of ethanol and tetrahydrofuran, and then adding an aqueous solution of sodium hydroxide at the temperature of not higher than 0 ℃; then the reaction mixture is moved to a temperature of not lower than 40 ℃ and stirred for at least 10 hours; the resulting solid was then filtered and washed with ethanol at least 3 times; the recovered solid was then suspended in acetone, then vigorously stirred and heated at reflux for at least 1 hour, the suspension was cooled to room temperature, filtered, washed with acetone, and dried under vacuum to give white solid supramolecular cup 2.
Preferably, in the step a, vacuum concentration treatment is adopted when the filtrate is concentrated, and the vacuum concentration treatment conditions are that the temperature is not higher than 50 ℃ and the vacuum degree is 0.09-0.1 MPa.
Preferably, in the step a, the concentration of the jones reagent adopted is not lower than 2.5mol/L, and the mixing mass ratio of the starting reaction raw materials and the jones reagent is 1.
Preferably, in step b, the product prepared in step a and the reactants of tin dichloride dihydrate are mixed in a mass ratio of 1.
Preferably, in step c, the reactant mixture mass ratio of the product prepared in step b and 2- (4-pyridylmethylene) malononitrile is 1.
Preferably, in step d, the reactant mixture mass ratio of the product prepared in step c and sodium hydroxide is 1.
Preferably, in step e, the mass ratio of the mixture of the product prepared in step b and 2- (3-pyridylmethylene) malononitrile is 1.
Preferably, in step f, the reactant mixture mass ratio of the product prepared in step e and sodium hydroxide is 1.
Preferably, in step d or in step f, before obtaining supramolecular cup 1 or supramolecular cup 2, a work-up operation is carried out, comprising addition of a large amount of water, washing with addition of a large amount of dichloromethane, washing with addition of a large amount of acetonitrile, vacuum drying, concentration under reduced pressure, obtaining supramolecular cup 1 or supramolecular cup 2.
The calixarene-derivatized supramolecular macrocyclic host compound has a hydrophobic cavity capable of accommodating guest molecules, can identify polar small molecules, comprises a compound containing 1, 4-dioxane in water pollutants, and can change fluorescence greatly after identifying the 1, 4-dioxane so as to detect whether the water contains the polar small molecule pollutants.
Compared with the prior art, the invention has the following obvious substantive characteristics and remarkable advantages:
1. the supermolecule cup 1 and the supermolecule cup 2 are novel in structure, have hydrophobic cavities, can identify polar small molecules, comprise water pollutants 1, 4-dioxane, have larger change in fluorescence after identifying the 1, 4-dioxane, and have potential application prospect in environmental pollution detection;
2. the synthetic route of the invention has simple and convenient process, easily obtained raw materials, mild reaction conditions, high yield and good repeatability.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a supramolecular cup 1.
FIG. 2 shows the nuclear magnetic carbon spectrum of the supramolecular cup 1.
FIG. 3 shows a high resolution mass spectrum of the supramolecular cup 1.
FIG. 4 is a nuclear magnetic spectrum of the micromolecular cup 1 (1 mmol/L, 500. Mu.L) complexed with the object (100 mmol/L, 5. Mu.L) for recognizing the polar small molecules. a) A supramolecular cup 1; b) Supramolecular cup 1 with tetrahydrofuran; c) Supramolecular cup 1 and tetrahydropyran; d) A supramolecular cup 1 with 1, 3-dioxane; e) A supramolecular cup 1 with 1, 4-dioxane; f) Supramolecular cup 1 and cyclohexene oxide.
FIG. 5 is a diagram of the rapid transition between different conformations of the supramolecular cup 1. The rapid change of dimer and vase conformation, which is characteristic of both supramolecular cup 1 and supramolecular cup 2, is illustrated for supramolecular cup 1.
FIG. 6 is a nuclear magnetic hydrogen spectrum of the supramolecular cup 2.
FIG. 7 is a nuclear magnetic carbon spectrum of the supramolecular cup 2.
FIG. 8 is a high resolution mass spectrum of the supramolecular cup 2.
FIG. 9 is a nuclear magnetic spectrum of the supermolecular cup 2 for identifying polar small molecules. For the recognition of water-soluble supermolecule cup 2 (1 mmol/L, 500. Mu.L) and guest small molecules (100 mmol/L, 5. Mu.L), the guests are sequentially from top to bottom: tetrahydropyran, cyclohexene oxide, cyclohexanol, cyclohexanone and sulfurized cyclopentane.
Fig. 10 is a nuclear magnetic hydrogen spectrum of intermediate product P4.
Fig. 11 is a nuclear magnetic hydrogen spectrum of intermediate product P3.
FIG. 12 is a graph showing fluorescence contrast between the host-guest complex of supramolecular cup 1 and supramolecular cup at 365 nm.
FIG. 13 shows the fluorescence spectra of the host and guest complexes of the supramolecular cup 1 and the supramolecular cup.
Detailed Description
The above-described embodiments are further illustrated below with reference to specific examples, in which preferred embodiments of the invention are detailed below:
the first embodiment is as follows:
in this embodiment, a calixarene-derivatized supramolecular macrocyclic host compound, which has a four-layer aromatic structure, can be dissolved in water, has a hydrophobic cavity structure capable of accommodating a guest molecule, and can selectively recognize a hydrophilic small molecule in water, has the following structural formula of supramolecular cup 1:
a preparation method of the supramolecular macrocyclic host compound derived from calixarene comprises the steps of taking resorcinol or derivatives thereof as initial reaction raw materials to prepare a water-soluble pyridyl supramolecular cup compound, introducing sodium carboxylate at the lower edge through oxidation reaction and hydrolysis reaction to achieve overall water solubility, introducing different pyridine groups at the upper edge through condensation with diamine to enable the middle part to be a benzimidazole group, enabling the addition of pyridine at the upper edge to reduce the caliber of a cavity, and slowing down object exchange. The synthesis steps are as follows:
the preparation method of the calixarene-derivatized supramolecular macrocyclic host compound comprises the following synthesis steps:
a. using resorcinol or its derivative P5 (200mg, 0.15mmol, 1eq.) as a raw material, adding Jones reagent (0.33ml, 10eq.) to 50mL of acetone solution of the raw material at 0 ℃, heating the reaction mixture to room temperature and stirring for 10 hours; the reaction was quenched by the addition of 5mL of 2-isopropanol and filtered; the filtrate was concentrated using a rotary evaporator to give a solid, and the solid was washed thoroughly 3 times with 50mL acetone and 50mL methanol, respectively, and dried under vacuum to give P4 (180 mg, yield 84%);
b. adding the product P4 prepared in the step a (200mg, 0.13mmol, 1eq.) to a round-bottomed flask cooled in an ice bath, taking the product P4 prepared in the step a and tin dichloride dihydrate as reactants, and suspending the product P4 in 20mL of ethanol precooled to 0 ℃ for stirring; to the suspension were slowly added 3.6g of tin dichloride dihydrate (169mol, 120eq.) and 5mL of concentrated hydrochloric acid having a mass fraction of 37.5%, and nitrogen gas was replaced 3 times; then the round bottom flask is immersed in an oil bath preheated to 110 ℃ and heated vigorously under reflux for 4 hours; the reaction mixture was cooled to room temperature, filtered, and the resulting solid was washed 3 times with 0 ℃ hydrochloric acid solution (50mL, 3mol/L), 5 times with 0 ℃ 10mL acetonitrile, and finally 5 times with 20mL diethyl ether to give P3 (150 mg) as a white solid after drying;
c. dissolving the product P3 prepared in step b and 2- (4-pyridylmethylene) malononitrile as reactants with 80mL of methanol, dissolving the product P3 prepared in step b (500mg, 1eq.) and adding 80mL of 25-28% by mass aqueous ammonia to obtain a white precipitate, then removing the solvent using a rotary evaporator, adding 100mL of methanol to the flask while adding 2- (4-pyridylmethylene) malononitrile (713mg, 12eq.) under nitrogen and vigorously stirring at 80 ℃ for 15 hours, then filtering to obtain a solid, washing the solid 3 times with 50mL of methanol, washing 2 times with water, washing 1 time with 50mL of dichloromethane, collecting the solid, and drying under vacuum to obtain P2.1 (412 mg, yield 65%);
d. adding the product P2.1 prepared in the step c (400mg, 0.24mmol, 1eq.) to another round-bottomed flask with a volume of 50mL, using the product P2.1 prepared in the step c and sodium hydroxide as reactants, adding 30mL of a mixed solvent in which ethanol and tetrahydrofuran are mixed in a volume ratio of 1; the reaction mixture was then brought to 40 ℃ and stirred for 10 hours; the resulting solid was then filtered and washed at least 3 times with 20mL of ethanol each time; the recovered solid was again suspended in 50mL of acetone, then vigorously stirred and heated at reflux for 1 hour, the suspension was cooled to room temperature, filtered, washed with 100mL of acetone, and dried under vacuum to give white solid supramolecular cup 1 (310 mg, 78% yield). The structural formula of the supermolecule cup 1 is as follows:
in this example, the intermediate product P4 was characterized, 1 HNMR(600MHz,DMSO-d 6 )δ12.27(s.4H),8.85(s.8H),8.29(s.4H),7.90(s.4H),5.60(s.4H),2.66(s.8H),2.24(s.8H). 13 C NMR(151MHz,DMSO-d 6 )δ174.36,155.55,154.52,140.25,136.14,126.45,122.55,116.93,33.49,32.45,27.21.
in this example, the intermediate product P3 was characterized, 1 H NMR(600MHz,DMSO-d 6 )δ7.81(s,4H),7.63(s,8H),7.22(s,4H),5.59(t,J＝9.5Hz,4H),4.06(d,J＝7.1Hz,8H),2.26(t,J＝7.6Hz,8H),1.19(t,J＝7.1Hz,12H).
in this example, the intermediate product P2.1 was characterized, 1 H NMR(600MHz,10％D 2 O/DMSO-d 6 ,δppm)8.58(d,8H),8.07(s,8H),7.85(m,12H),7.72(s,4H),5.61(t,4H),4.05(t,8H),2.62(t,8H),2.29(t,8H),1.18(t,12H). 13 C NMR(151MHz,DMSO-d6/10％D2O,δppm)173.29,155.96,150.10,149.74,136.84,135.29,135.17,125.00,124.36,117.32,60.63,50.54,33.36,32.72,27.49,18.56,14.46.HRMS(ESI):Calcd for chemical formula C 96 H 76 N 12 O 16 :1652.5502,found:1653.56[M+H] + .
in this example, the final product supramolecular cup 1 was characterized, 1 H NMR(600MHz,D 2 O/10％DMSO-d 6 )δ8.78(d,8H),7.87-7.72(m,20H),7.63(s,4H),5.67(t,4H),2.64(t,8H),2.25(t,8H). 13 C NMR(151MHz,D 2 O/10％DMSO-d 6 )δ183.43,166.41,157.19,150.65,149.80,141.32,137.05,125.77,122.40,118.52,111.75,39.09,37.43,35.04,29.85.HRMS(ESI):Calcd for chemical formula C 88 H 56 N 12 O 16 :1540.4250,found:1538.41[M-2H] 2- 。
experimental test analysis:
supermolecule cup 1 (16.29mg, 10.00. Mu. Mol) was added to a 25mL sample bottle, 10mL of heavy water was added thereto, and the solution was dissolved by sonication to give a clear and transparent pale yellow solution (1 mmol/L).
500 mu L of the solution is added into a nuclear magnetic tube, 5 mu L of guest heavy water solution with the concentration of 100mmol/L is added into the nuclear magnetic tube, the nuclear magnetic resonance hydrogen spectrum of 298K is measured on a Bruker AVANCE III HD 600M machine after the solution is mixed, the scanning width is set as 20, the center is 5, and the scanning times are 64 times.
Due to the recognition ability of the supramolecular cup 1 for polar small molecules, and many polar small molecules are environmental pollutants due to their high hydrophilicity. The host-object recognition characteristic of the supermolecule cup is applied to the field of environmental pollutant adsorption, and pollutants with strong water solubility are adsorbed by the supermolecule host to realize the pollutant detection function.
FIG. 1 is a nuclear magnetic hydrogen spectrum of a supramolecular cup 1. FIG. 2 shows the nuclear magnetic carbon spectrum of the supramolecular cup 1. FIG. 3 shows a high resolution mass spectrum of the supramolecular cup 1. FIG. 4 is a nuclear magnetic spectrum of the complex of supermolecule cup 1 (1 mmol/L, 500. Mu.L) and guest (100 mmol/L, 5. Mu.L) for the recognition of polar small molecules. a) A supramolecular cup 1; b) Supramolecular cup 1 with tetrahydrofuran; c) Supramolecular cup 1 and tetrahydropyran; d) A supramolecular cup 1 with 1, 3-dioxane; e) Supramolecular cup 1 with 1, 4-dioxane; f) Supramolecular cup 1 and cyclohexene oxide. FIG. 5 is a diagram showing the rapid change of conformation of the supramolecular cup 1 from different conformation to dimer and vase conformation, see FIG. 5. Fig. 10 is a nuclear magnetic hydrogen spectrum of intermediate product P4. Fig. 11 is a nuclear magnetic hydrogen spectrum of intermediate product P3.
Due to the high shielding effect of the host cavity in the compound structure, the chemical shift of the hydrogen of the guest molecule can move to a high field in the nuclear magnetic spectrum, which often causes the nuclear magnetic signal of the hydrogen of the guest molecule to appear after 0ppm, see fig. 4. The state of pure 1 in water is a rapid change between "dimer" and "vase" conformations, as shown in figure 3. The result of this rapid conformational change is that most of the characteristic peaks of the host are not observed in the nuclear magnetic hydrogen spectrum, see a) in fig. 3.
500. Mu.L of the above solution was added to a 2mL sample bottle. Then 500. Mu.L and 5. Mu.L of the above solution in the supermolecular cup 1, and 100mmol/L of 1, 4-dioxane guest heavy water solution are added into a 2mL sample bottle, and the sample bottle with the guest solution added therein is observed under an ultraviolet lamp with a wavelength of 365nm, so that the difference between the fluorescence of the sample bottle without the guest solution can be observed, as shown in FIG. 12.
Taking the solution of the super-molecular cup 1 and the host-guest complex solution of the super-molecular cup 1, and testing the fluorescence absorption wavelength by using a fluorescence spectrometer to find that the two solutions are different, wherein the method can be used for detecting whether the water contains polar small-molecule pollutants or not, and is shown in figure 13.
In the preparation method of the supermolecule with good water solubility, the pyridine group is introduced to the upper edge of the water-soluble supermolecule cup, so that the depth of the cavity is increased, the in-and-out exchange of the object is slowed down, and the hydrophilic micromolecules can be identified.
The second embodiment:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a calixarene-derivatized supramolecular macrocyclic host compound, which has a four-layer aromatic structure, can be dissolved in water, has a hydrophobic cavity structure capable of accommodating a guest molecule, and can selectively recognize a hydrophilic small molecule in water, has the following structural formula of supramolecular cup 2:
a preparation method of the supramolecular macrocyclic host compound derived from calixarene comprises the steps of taking resorcinol or derivatives thereof as initial reaction raw materials to prepare a water-soluble pyridyl supramolecular cup compound, introducing sodium carboxylate at the lower edge through oxidation reaction and hydrolysis reaction to achieve overall water solubility, introducing different pyridine groups at the upper edge through condensation with diamine to enable the middle part to be a benzimidazole group, enabling the addition of pyridine at the upper edge to reduce the caliber of a cavity, and slowing down object exchange. The synthesis steps are as follows:
the preparation method of the calixarene-derivatized supramolecular macrocyclic host compound comprises the following synthesis steps:
A. the step is the same as the first embodiment;
B. the step is the same as the first embodiment;
C. dissolving the product P3 prepared in step B and 2- (3-pyridylmethylene) malononitrile as reactants, the product P3 prepared in step B (500mg, 1eq.) with 80mL of methanol and adding 8mL of ammonia water with a mass fraction of 25-28% to give a white precipitate, then removing the solvent using a rotary evaporator, adding 100mL of methanol to the flask while adding 2- (3-pyridylmethylene) malononitrile (713mg, 12eq.) under nitrogen and vigorously stirring at 80 ℃ for 15 hours, then filtering to give a solid, washing the solid 3 times with 50mL of methanol, 2 times with 50mL of acetonitrile, collecting the solid, and drying under vacuum to give P2.2 (381 mg, yield 60%);
D. adding the product P2.2 (400mg, 0.24mmol, 1eq.) prepared in step C to another round-bottomed flask having a volume of 50mL, using the product P2.2 prepared in step C and sodium hydroxide as reactants, adding 30mL of a mixed solvent in which ethanol and tetrahydrofuran are mixed in a volume ratio of 1; the reaction mixture was then brought to 40 ℃ and stirred for 10 hours; then the solid obtained is filtered and washed with ethanol for 3 times, each time using 30mL of ethanol; the recovered solid was again suspended in 50mL of acetone, then vigorously stirred and heated at reflux for 1 hour, the suspension was cooled to room temperature, filtered, washed with 100mL of acetone, and dried under vacuum to give white solid supramolecular cup 2 (328 mg, 82% yield). The structural formula of the supermolecule cup 2 is as follows:
in this example, the intermediate product P2.2 was characterized, 1 H NMR(600MHz,DMSO-d 6 /D 2 O 10％)δ9.06(s,4H),8.51(t,4H),8.16(t,4H),8.04(s,8H),7.85(s,4H),7.72(s,4H),7.39-7.37(m,4H)5.62(t,4H),4.03(t,8H),1.74(m,8H). 13 C NMR(151MHz,DMSO-d6/D 2 O 10％)δ174.68,173.28,155.98,150.84,150.03,149.31,147.06,135.18,133.89,125.32,125.00,124.50,117.34,60.61,55.05,38.93,33.37,32.70,27.50,14.48.HRMS(ESI):Calcd for chemical formula C 96 H 76 N 12 O 16 ,found:1653.56[M+H] + .
in this example, the final product supramolecular cup 2 was characterized, 1 HNMR(600MHz,D 2 O/10％DMSO-d 6 )δ9.05(d,4H),8.38(t,4H),8.22(t,4H),7.83-7.74(m,12H),7.61(s,4H),7.32(t,4H),5.62(t,4H),2.61(t,8H),2.18(t,8H). 13 C NMR(151MHz,D 2 O/10％DMSO-d 6 )δ155.78,150.39,149.85,149.40,136.48,135.26,124.84,120.19,117.27,45.30,40.04,39.93,39.90,39.79,39.65,39.51,39.37,39.23,39.09,33.01,31.23,29.13.HRMS(ESI):Calcd for chemical formula C 88 H 56 N 12 O 16 :1540.4250,found:1538.41[M-2H] 2- .
experimental test analysis:
supermolecule cup 2 (16.29mg, 10.00. Mu. Mol) was added to a 25mL sample bottle, 10mL of heavy water was added thereto, and the mixture was dissolved by sonication to give a clear and transparent pale yellow solution (1 mmol/L).
Adding 500 mu L of the solution into a nuclear magnetic tube, adding 5 mu L of 100mmol/L object heavy water solution into the nuclear magnetic tube, mixing the solutions, and measuring a 298K nuclear magnetic resonance hydrogen spectrum on a Brukeravence III HD 600M machine, wherein the scanning spectrum width is set as 20, the center is 5, and the scanning times are 64.
Due to the recognition ability of the supramolecular cup 2 for polar small molecules, and many polar small molecules are environmental pollutants due to their high hydrophilicity. The host-object recognition characteristic of the supermolecule cup is applied to the field of environmental pollutant adsorption, and pollutants with strong water solubility are adsorbed by the supermolecule host to realize the pollutant detection function.
FIG. 5 is a diagram of the rapid transition between different conformations of the supramolecular cup 1. The rapid change of dimer from vase conformation is also present in supramolecular cup 2. FIG. 6 is a nuclear magnetic hydrogen spectrum of the supramolecular cup 2. FIG. 7 is a nuclear magnetic carbon spectrum of the supramolecular cup 2. FIG. 8 is a high resolution mass spectrum of the supramolecular cup 2. FIG. 9 is a nuclear magnetic spectrum of the supermolecule cup 2 for identifying the polar small molecules. For the recognition of water-soluble supermolecule cup 2 (1 mmol/L, 500. Mu.L) and guest small molecules (100 mmol/L, 5. Mu.L), the guests are sequentially from top to bottom: tetrahydropyran, cyclohexene oxide, cyclohexanol, cyclohexanone and sulfurized cyclopentane.
According to the preparation method of the supermolecule with good water solubility, the pyridine group is introduced to the upper edge of the water-soluble supermolecule cup, so that the depth of a cavity is increased, the in-and-out exchange of an object is slowed down, and the hydrophilic micromolecules are identified. The present example supramolecular cup dissolved in water provides a hydrophobic cavity that can accommodate guest molecules.
In summary, in the preparation method of the water-soluble pyridyl supermolecule cup of the above embodiment, resorcinol derivative is used as a starting material, a sodium carboxylate is introduced at the lower edge through an oxidation reaction and a hydrolysis reaction to achieve overall water solubility, and a pyridine group different from that introduced by condensation with diamine is introduced at the upper edge, so that on one hand, the middle part is divided into a benzimidazole group, and on the other hand, the addition of pyridine at the upper edge reduces the aperture of a cavity, and slows down object exchange. The preparation method has the advantages of simple route and process, easily obtained raw materials, mild reaction conditions, high yield and good repeatability. The supermolecule cup compound of the embodiment has good water solubility, simultaneously provides a hydrophobic cavity capable of containing guest molecules, can selectively identify hydrophilic small molecules in water, including water pollutants 1, 4-dioxane, and has a potential prospect of being applied to environmental pollution detection, and fluorescence can be greatly changed after the 1, 4-dioxane is identified.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made based on the spirit and principle of the technical solution of the present invention shall be equivalent replacement, so long as the invention is in accordance with the purpose of the present invention, and the technical principle and the inventive concept of the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. A calixarene-derivatized supramolecular macrocyclic host compound, characterized by: the water-soluble organic polymer has at least four-layer aromatic structure, can be dissolved in water, has a hydrophobic cavity structure capable of accommodating guest molecules, and can selectively recognize hydrophilic small molecules in water, and the structure of the water-soluble organic polymer is at least one of the following supermolecule cup 1 and supermolecule cup 2:
the structural formula of the molecular cup 1 is as follows:
the structural formula of the molecular cup 2 is as follows:
2. process for the preparation of calixarene-derivatized supramolecular macrocyclic host compound according to claim 1, characterized by comprising the following synthetic steps:
a. using resorcinol derivative as raw material, adding Jones reagent into acetone solution of the raw material at 0 deg.C or higher, heating the reaction mixture to room temperature and stirring for at least 10 hr; the reaction was quenched by addition of 2-isopropanol and filtered; concentrating the filtrate by using a rotary evaporator to obtain a solid, thoroughly washing the solid with acetone and methanol for at least 3 times respectively, and then drying; the structural formula of the resorcinol derivative is as follows:
b. Adding the product prepared in the step a and tin dichloride dihydrate into a round-bottom flask cooled in an ice bath by taking the product prepared in the step a and the tin dichloride dihydrate as reactants, and suspending the product in ethanol pre-cooled to be not higher than 0 ℃ for stirring; slowly adding tin dichloride dihydrate and concentrated hydrochloric acid with the mass fraction not less than 20% into the suspension, and replacing nitrogen for at least 3 times; then immersing the round-bottom flask into an oil bath preheated to not lower than 110 ℃, and heating and refluxing vigorously for at least 4 hours; cooling the reaction mixture to room temperature, filtering, washing the obtained solid with hydrochloric acid solution with the concentration of not higher than 3mol/L for at least 3 times, then washing with acetonitrile with the temperature of not higher than 0 ℃ for at least 5 times, finally washing with diethyl ether for at least 5 times, and then drying;
c. dissolving the product prepared in the step b and 2- (4-pyridylmethylene) malononitrile as reactants with methanol, and adding 25-28% by mass of aqueous ammonia to obtain a white precipitate, then removing the solvent using a rotary evaporator, adding methanol to the flask while adding 2- (4-pyridylmethylene) malononitrile under nitrogen and vigorously stirring at a temperature of not higher than 80 ℃ for at least 15 hours, then filtering to obtain a solid, washing the solid with methanol at least 3 times, water at least 2 times, dichloromethane at least 1 time, collecting the solid, and drying under vacuum;
d. adding the product prepared in the step c and sodium hydroxide as reactants into another round-bottom flask, adding a mixed solvent of ethanol and tetrahydrofuran, and then adding an aqueous solution of sodium hydroxide at a temperature of not higher than 0 ℃; then the reaction mixture is transferred to the temperature of not lower than 40 ℃ and stirred for at least 10 hours; the resulting solid was then filtered and washed with ethanol at least 3 times; suspending the recovered solid in acetone, then stirring vigorously and heating under reflux for at least 1 hour, cooling the suspension to room temperature, filtering, washing with acetone, and drying under vacuum to obtain white solid supramolecular cup 1;
e. dissolving the product prepared in the step b and 2- (3-pyridylmethylene) malononitrile as reactants with methanol, adding 25-28 mass% of ammonia water to obtain a white precipitate, removing the solvent using a rotary evaporator, adding methanol to a flask while adding 2- (3-pyridylmethylene) malononitrile, vigorously stirring under nitrogen at a temperature of not higher than 80 ℃ for at least 15 hours, filtering to obtain a solid, washing the solid with methanol at least 3 times, washing acetonitrile at least 2 times, collecting the solid, and drying under vacuum;
f. adding the product prepared in the step e into the other round-bottom flask by taking the product prepared in the step e and sodium hydroxide as reactants, adding a mixed solvent of ethanol and tetrahydrofuran, and then adding an aqueous solution of sodium hydroxide at the temperature of not higher than 0 ℃; then the reaction mixture is transferred to the temperature of not lower than 40 ℃ and stirred for at least 10 hours; the resulting solid was then filtered and washed with ethanol at least 3 times; the recovered solid was then suspended in acetone, then vigorously stirred and heated at reflux for at least 1 hour, the suspension was cooled to room temperature, filtered, washed with acetone, and dried under vacuum to give white solid supramolecular cup 2.
3. Process for the preparation of calixarene-derivatized supramolecular macrocyclic host compound according to claim 2, characterized in that: in the step a, vacuum concentration treatment is adopted when filtrate is concentrated, and the conditions of the vacuum concentration treatment are that the temperature is not higher than 50 ℃ and the vacuum degree is 0.09-0.1 MPa; the concentration of the adopted jones reagent is not lower than 2.5mol/L, and the mixing mass ratio of the initial reaction raw materials to the jones reagent is 1.
4. Process for the preparation of calixarene-derivatized supramolecular macrocyclic host compound according to claim 2, characterized in that: in step b, the mass ratio of the product prepared in step a to the reactants of tin dichloride dihydrate was 1.
5. A method for the preparation of calixarene-derivatized supramolecular macrocyclic host compound as claimed in claim 2, characterized in that: in step c, the reactant mixture mass ratio of the product prepared in step b and 2- (4-pyridylmethylene) malononitrile is 1;
or in the step d, the reactant mixture mass ratio of the product prepared in the step c and the sodium hydroxide is 1.
6. A method for the preparation of calixarene-derivatized supramolecular macrocyclic host compound as claimed in claim 2, characterized in that: in step e, the mass ratio of the mixture of the product prepared in step b and 2- (3-pyridylmethylene) malononitrile is 1;
or in step f, mixing the product prepared in step e and reactants of sodium hydroxide in a mass ratio of 1.
7. A method for the preparation of calixarene-derivatized supramolecular macrocyclic host compound as claimed in claim 2, characterized in that: in step d or step f, before obtaining supramolecular cup 1 or supramolecular cup 2, post-treatment operations are carried out, including adding a large amount of water, adding a large amount of dichloromethane for washing, adding a large amount of acetonitrile for washing, vacuum drying, and vacuum concentration to obtain supramolecular cup 1 or supramolecular cup 2.
8. Use of calixarene-derivatized supramolecular macrocyclic host compound as claimed in claim 1, characterized in that: the calixarene-derivatized supramolecular macrocyclic host compound has a hydrophobic cavity capable of accommodating guest molecules and is used for identifying polar small molecule 1, 4-dioxane.
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