CN115626930B - Synthesis method and application of seven-membered cucurbituril-trimeric indene derivative - Google Patents

Synthesis method and application of seven-membered cucurbituril-trimeric indene derivative Download PDF

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CN115626930B
CN115626930B CN202211288160.1A CN202211288160A CN115626930B CN 115626930 B CN115626930 B CN 115626930B CN 202211288160 A CN202211288160 A CN 202211288160A CN 115626930 B CN115626930 B CN 115626930B
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indene
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CN115626930A (en
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董南
喻琼林
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Guizhou University
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Abstract

The invention discloses a synthesis method and application of a seven-membered cucurbituril-trioxane derivative, wherein the seven-membered cucurbituril-trioxane derivative is obtained by derivatizing a monohydroxy seven-membered cucurbituril into 4-vinylbenzyloxy seven-membered cucurbituril, derivatizing trioxane into 2-iodo-5, 5 ', 10', 15 '-hexahexyl trioxane, and synthesizing the seven-membered cucurbituril-trioxane derivative by substitution reaction of the 4-vinylbenzyloxy seven-membered cucurbituril and the 2-iodo-5, 5', 10 ', 15' -hexahexyl trioxane. The seven-membered cucurbituril-trimeric indene derivative has good organic solubility, can be dissolved in organic solvents such as dichloromethane, chloroform and the like, and changes the bottleneck that cucurbituril cannot be dissolved in the organic solvents. The seven-membered cucurbituril-trimeric indene derivative is used as a stationary phase, and a high-performance capillary gas chromatographic column is prepared by a static coating method, so that xylene isomers and aromatic amine isomer compounds which are difficult to separate can be effectively separated, and the separation performance is better than that of a commercial chromatographic column HP-5.

Description

Synthesis method and application of seven-membered cucurbituril-trimeric indene derivative
Technical Field
The invention relates to a seven-membered cucurbituril-trimeric indene derivative, a synthesis method and application thereof.
Background
Cucurbiturils (CB [ n ]) are a class of open ended, barreled macrocyclic compounds bridged by n glycosidic urea units and 2n methylene groups, having a hydrophobic cavity structure and an electron-rich terminal carbonyl group. The host molecule can be used for generating host-guest interaction with the guest molecule through cavity inclusion or hydrogen bond of a port, van der Waals force, dipole-dipole action, pi-pi accumulation and the like, and has stronger molecular recognition capability. However, the cucurbiturils have strong polarity, six-membered and eight-membered cucurbiturils are soluble in strong acids (such as hydrochloric acid), and five-membered and seven-membered cucurbiturils are soluble in water and strong acids. The common five, six, seven and eight cucurbiturils are all insoluble in organic solvents, which brings a restriction for the preparation of new materials based on cucurbiturils. The trimeric indene molecule is characterized in that three fluorene shares a benzene ring in the middle, so that a condensed ring compound with a Y-shaped structure is formed, and the condensed ring compound has good rigid plane and large pi electron delocalization property. The C2, C5, C7, C10, C12, C15 and other sites of the trimeric indene are easy to modify, and the pi-system expanded trimeric indene derivative is obtained by introducing different end group functional groups, so that the corresponding physicochemical properties are obtained. Because of the relatively poor solubility, alkyl chains (mostly hexyl chains) may be introduced at the C5, C10, and C15 positions to increase solubility. Meanwhile, the C2, C7 and C12 positions can be brominated through electrophilic substitution reaction, then an aromatic ring or other pi conjugated groups can be easily linked to a trimeric indene structure through coupling reaction, and a pi conjugated system is increased through expansion of a molecular scale in a three-dimensional direction.
At present, the derivative synthesized by cucurbituril and trioxyindene with better organic solubility in the prior art has not been found, and the developed seven-membered cucurbituril-trioxyindene derivative has better organic solubility and can be dissolved in medium-polarity organic solvents such as chloroform, dichloromethane and the like. The compound is used as a raw material, and a capillary gas chromatographic column with high performance is prepared by a static coating method, so that the compound can be used for separating isomer compounds which are difficult to separate by a conventional capillary commodity column.
Disclosure of Invention
The invention aims to synthesize a seven-membered cucurbituril-trimeric indene derivative which is easy to dissolve in an organic solvent, and the synthesized compound is used as a capillary gas chromatography stationary phase to synthesize a capillary gas chromatography column with high-performance separation characteristic, and is used for separating an isomer compound which is difficult to separate by a conventional commodity column.
The technical scheme of the invention is as follows: an organic soluble heptatomic cucurbituril-trimeric indene derivative with a molecular formula of C 114 H 138 N 28 O 15 The structural formula is as follows:
。
the synthesis method of the organic soluble heptatomic cucurbituril-trioxane derivative comprises the steps of derivatizing monohydroxy heptatomic cucurbituril into 4-vinylbenzyloxy heptatomic cucurbituril, derivatizing trioxyindene into 2-iodo-5, 5', 10',15 '-hexahexyl trioxyindene, and synthesizing the 4-vinylbenzyloxy heptatomic cucurbituril and the 2-iodo-5, 5',10 ', 15' -hexahexyl trioxyindene into the heptatomic cucurbituril-trioxyindene derivative through substitution reaction.
The synthesis method of the 4-vinylbenzyloxy seven-membered cucurbituril specifically comprises the following steps:
dispersing monohydroxy seven-membered cucurbituril in anhydrous N, N-dimethylformamide under stirring in a two-neck flask, adding anhydrous dimethyl sulfoxide, stirring continuously until the monohydroxy seven-membered cucurbituril is dissolved, and adding the mixture into N 2 Cooling the reaction to 0 ℃ under protection, adding NaH, stirring to react for 3-5 h, adding 4-vinylbenzyl chloride, removing ice bath to restore room temperature to react for 14-18 h, adding diethyl ether to precipitate reaction liquid, repeatedly filtering and washing the obtained precipitate with methanol for 2-4 times, and finally obtaining light yellow solid, namely the 4-vinylbenzyloxy seven-membered melon ring.
Specifically, the synthesis method of the 4-vinylbenzyloxy seven-membered cucurbituril specifically comprises the following steps:
in a two-neck flask of 100 mL, a monohydroxy seven-membered cucurbituril 500 mg was dispersed in 7.5mL anhydrous N, N-dimethylformamide with stirring, and then added37.5mL anhydrous dimethyl sulfoxide, stirring until the monohydroxy seven-membered melon ring is dissolved, and adding the mixture into N 2 Cooling the reaction to 0 ℃ under protection, adding NaH 850 mg, stirring to react for 4 h, adding 1550 mu L of 4-vinylbenzyl chloride, removing ice bath to restore room temperature to react for 16 h, adding 50 mL diethyl ether to precipitate reaction liquid, repeatedly filtering and washing the obtained precipitate with 10 mL methanol for 3 times, and finally obtaining a light yellow solid, namely the 4-vinylbenzyloxy heptatomic melon ring.
The synthesis method of the 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene specifically comprises the following steps:
(1) Accurately weighing 1-indenone, adding the 1-indenone into a mixed solution of glacial acetic acid and concentrated hydrochloric acid, dissolving the mixture, then placing the mixture in a constant-temperature oil bath pot, slowly heating the mixture to 110-130 ℃, keeping the temperature to reflux for 22-26 hours, rapidly pouring the mixture into an ice-water mixture while hot, rapidly stirring the mixture while pouring the mixture into the mixture, adding anhydrous sodium carbonate into the solution after uniform distribution, neutralizing unreacted acid, stirring the solution while adding, testing the solution to be neutral by using pH test paper, standing the solution for one hour, separating out yellow precipitate, performing vacuum filtration on the separated yellow precipitate, repeatedly washing the yellow precipitate by using secondary water for 2-4 times, repeatedly washing the precipitate by using acetone and dichloromethane each time until the precipitate is light yellow, and drying the precipitate to obtain a product A;
(2) Adding a product A and anhydrous tetrahydrofuran into a 50mL two-neck round bottom flask, stirring in an ice-water mixture under the protection of nitrogen, slowly dropwise adding n-butyllithium into the flask when the temperature in the flask is reduced to 0 ℃, reacting at 0 ℃, slowly dropwise adding 1-bromohexane, reacting at room temperature for 3-5h, reducing the system temperature to 0 ℃, slowly dropwise adding n-butyllithium into the flask, reacting at 0 ℃ for 1-2 h, slowly dropwise adding 1-bromohexane, and reacting at room temperature for 10-14h to obtain a product B;
(3) Quenching the product B by using an ammonium chloride saturated solution, extracting with dichloromethane three times, 40-60mL each time, combining organic phases, adding anhydrous sodium sulfate to dry the organic phases, filtering, and concentrating to 1.2 mL at 40 ℃ by using a rotary evaporator to obtain a product C;
(4) Adding 1.4g of silica gel into the C product, fully adsorbing the C product by the silica gel, drying the silica gel on a water bath kettle at 60 ℃ and taking the silica gel as a sample for column chromatography, taking 150-300 meshes of silica gel as a stationary phase, taking petroleum ether as eluent to separate the treated sample, and collecting eluent which is confirmed by thin layer chromatography and contains target components 5,5 ', 10 ', 15 ' -hexahexyl trimeric indene in the separation process. Collecting eluent, spin-drying the eluent by a rotary evaporator, and vacuum drying to obtain bright yellow solid, namely D product;
(5) Dissolving the D product in dichloromethane, slowly dropwise adding concentrated nitric acid at 0 ℃ for reaction for 1-3h, extracting with dichloromethane twice, each time for 40-60mL, combining organic phases, washing the organic phases with 50-70mL saturated sodium chloride solution, drying the organic phases with anhydrous sodium sulfate, filtering, taking filtrate, spin-drying with a rotary evaporator, taking 200-mesh silica gel as a stationary phase, and separating eluent as petroleum ether, wherein the mixed solution of dichloromethane=5 mL and 1mL by column chromatography to obtain yellow solid, namely E product;
(6) Taking E product, iron powder and NH 4 CI 4 Dissolving in 99.7% absolute ethyl alcohol, heating and refluxing for reaction for 3-5h at 80 ℃, cooling the reaction, filtering out solid residues, spin-drying filtrate by a rotary evaporator, dissolving with ethyl acetate for 3 times, 40mL each time, washing the combined ethyl acetate solution with 80mL saturated sodium chloride solution, drying with 12g absolute sodium sulfate, and spin-drying extract by the rotary evaporator to obtain F product;
(7) Separating the F product on a 150-350 mesh silica gel column, wherein the eluent is petroleum ether and dichloromethane mixed solution = 2mL:1mL, tracking the target component aminotriazine by thin layer chromatography, and collecting corresponding eluent to obtain a target compound aminotriazine, namely G product;
(8) Dissolving G in dichloromethane, adding silica gel, spin-drying in a rotary evaporator to obtain powder, dissolving the powder in water, freezing to 0deg.C, adding concentrated hydrochloric acid, stirring, adding aqueous solution of sodium nitrite, reacting at 0deg.C for 0.5-1.5 hr, adding aqueous solution of potassium iodide, reacting for 8-14 hr, adding saturated sodium bisulphite, quenching, adding 70mL of dichloromethane, extracting for 1 time, collecting organic phase, drying with anhydrous sodium sulfate, spin-drying, separating with 150-350 mesh silica gel column as stationary phase, separating with column chromatography, collecting eluent of target compound with petroleum ether by thin layer tracing, spin-drying eluent with rotary evaporator to obtain pale pink solid, namely 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene.
Specifically, the synthesis method of the 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene specifically comprises the following steps:
(1) Accurately weighing 20.0g of 1-indenone, adding the 1-indenone into a mixed solution of 120 mL glacial acetic acid and 60 mL concentrated hydrochloric acid, dissolving, placing the mixed solution in a constant-temperature oil bath pot, slowly heating to 120 ℃, keeping the temperature to reflux 24 h, rapidly pouring the mixed solution into 1L of ice-water mixture while hot, rapidly stirring while pouring the mixed solution, adding 13.5g of anhydrous sodium carbonate into the solution after uniform distribution, neutralizing the unreacted acid, stirring while adding, testing the solution to be neutral by using pH test paper, standing for one hour, precipitating yellow precipitate, repeatedly washing the precipitated yellow precipitate with secondary water for 3 times after decompression and suction filtration, repeatedly washing the precipitate to be light yellow by using acetone and dichloromethane each time, and drying to obtain a product A;
(2) Adding 0.732g of product A and 12mL of anhydrous tetrahydrofuran into a 50mL two-neck round bottom flask, placing the two-neck round bottom flask into an ice-water mixture under the protection of nitrogen gas, stirring, slowly dripping 5mL of n-butyllithium into the flask when the temperature in the flask is reduced to 0 ℃, reacting for 1.5h at the temperature of 0 ℃, slowly dripping 1.2mL of 1-bromohexane, reacting for 4h at the room temperature, reducing the temperature of the system to 0 ℃, slowly dripping 5mL of n-butyllithium into the flask, reacting for 1.5h at the temperature of 0 ℃, slowly dripping 1.2mL of 1-bromohexane, and reacting for 12h at the room temperature to obtain a product B;
(3) Quenching the product B by using 60mL of ammonium chloride saturated solution, extracting with dichloromethane three times, 50mL each time, combining organic phases, adding 15g of anhydrous sodium sulfate to dry the organic phases, filtering, and concentrating to 1.2mL at 40 ℃ by using a rotary evaporator to obtain a product C;
(4) Adding 1.4g of silica gel into the C product, fully adsorbing the C product by the silica gel, drying the silica gel on a water bath kettle at 60 ℃ and taking the silica gel as a sample for column chromatography, taking 150-300 meshes of silica gel as a stationary phase, taking petroleum ether as eluent to separate the treated sample, collecting eluent which is confirmed by thin layer chromatography and contains target components 5,5 ', 10 ', 15 ' -hexahexyl trimeric indene in the separation process, collecting the eluent, spin-drying the solvent of the eluent by a rotary evaporator, and then carrying out vacuum drying to obtain a bright yellow solid, namely a D product;
(5) Dissolving 1g of the D product in 10mL of dichloromethane, slowly dropwise adding 0.25mL of concentrated nitric acid at 0 ℃, reacting for 2h, extracting twice with dichloromethane, 50mL each time, combining organic phases, washing the organic phases with 60mL of saturated sodium chloride solution, drying the organic phases with 15g of anhydrous sodium sulfate, filtering, taking filtrate, spin-drying with a rotary evaporator, and carrying out column chromatography separation on a mixed solution of 200-mesh silica gel serving as a stationary phase and eluent of petroleum ether, dichloromethane=5mL:1mL to obtain yellow solid, namely E product;
(6) Taking 0.73g of E product, 0.46g of iron powder and NH 4 CI 4 0.4g of the mixture is dissolved in 10 mL of 99.7% ethanol, the mixture is heated and refluxed for 4 hours at 80 ℃, after the reaction is cooled, solid residues are filtered, the filtrate is dried by a rotary evaporator in a spinning way, the filtrate is dissolved for 3 times by ethyl acetate, each time 40 and mL are dissolved, the ethyl acetate solution is combined and washed by 80 and mL saturated sodium chloride solution, and then the mixture is dried by 12 g of anhydrous sodium sulfate, and then the solvent is dried by the rotary evaporator in a spinning way, so that the F product is obtained;
(7) Separating 1.21G of F product on 200-300 mesh silica gel column, wherein the eluent is petroleum ether, dichloromethane=2mL:1mL, tracking target component amino-trimeric indene by thin layer chromatography, and collecting corresponding eluent to obtain target compound amino-trimeric indene, namely G product;
(8) Dissolving G0.4. 0.4G in 1.8mL of dichloromethane, adding 1.2G of silica gel, spin-drying in a rotary evaporator to obtain powder, dissolving the powder in 6mL of water, freezing to 0 ℃, adding 6mL of concentrated hydrochloric acid, stirring vigorously, adding 2.5mL of aqueous solution of 0.9 mmol of sodium nitrite, reacting at 0 ℃ for 1h, adding 3mL of aqueous solution of 1.87 mmol of potassium iodide, reacting for 12h, adding 20mL of saturated sodium bisulphite after the reaction is finished, performing quenching reaction, adding 70mL of dichloromethane, extracting for 1 time, collecting an organic phase, drying with 7.5G of anhydrous sodium sulfate, spin-drying, separating by using a 200-300 mesh silica gel column as a stationary phase, performing column chromatography, eluting the eluent is petroleum ether, carrying out thin-layer tracking, collecting eluent of a target compound, and spin-drying the eluent by the rotary evaporator to obtain light pink solid, namely the 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene.
The synthesis method of the seven-membered cucurbituril-trimeric indene derivative specifically comprises the following steps:
adding 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene, 4-vinylbenzyloxy heptatomic melon ring, anhydrous N, N-dimethylformamide, triethylamine, palladium acetate and tri (4-methoxyphenyl) phosphine into a 25mL three-neck flask in an anhydrous anaerobic system, stirring and heating to 75-95 ℃ to react for 16-20h, stopping heating, cooling to room temperature, pouring into water, extracting with chloroform for 3 times, 40-60mL each time, merging organic phases, washing the organic phases with water for 3 times, 15-25mL each time, drying with anhydrous sodium sulfate, drying the organic phases with a rotary evaporator, separating with a silica gel as a stationary phase by a column chromatography, eluting with dichloromethane: methanol=20-35 mL, carrying out thin-layer tracking and collecting eluent of a target compound, and carrying out rotary evaporation on the eluent to obtain a dark yellow solid, namely the heptatomic melon ring-trimeric indene derivative.
Specifically, the synthesis method of the seven-membered cucurbituril-trimeric indene derivative specifically comprises the following steps:
adding 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene 70-90 mg, 4-vinylbenzyloxy heptatomic melon ring 320-350 mg, anhydrous N, N-dimethylformamide 4-6mL, triethylamine 1-2mL, palladium acetate 3-5mg and 10-14mg of tris (4-methoxyphenyl) phosphine into a 25mL three-neck flask, stirring and heating to 85-90 ℃ for 17-19h, stopping heating, cooling to room temperature, pouring into 10 mL water, extracting with chloroform for 3 times, 45-55 mL each time, merging organic phases, washing the organic phases with water for 3 times, each time with 18-22 mL, drying with 16-20 g anhydrous sodium sulfate, spin-drying the organic phases with a rotary evaporator, separating with silica gel column chromatography, eluting with dichloromethane=30 mL of methanol, 1mL, tracking and collecting eluent of a target compound in a thin layer, spin-drying the eluent with a rotary evaporator to obtain the heptatomic indene derivative.
More specifically, the synthesis method of the seven-membered cucurbituril-trimeric indene derivative specifically comprises the following steps:
adding 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene 80 mg, 4-vinylbenzyloxy heptatomic melon ring 336 mg, anhydrous N, N-dimethylformamide 5mL, triethylamine 1.5mL, palladium acetate 4 mg and 12mg of tris (4-methoxyphenyl) phosphine into a 25mL three-neck flask in an anhydrous anaerobic system, stirring and heating to 85 ℃ to react for 18 hours, stopping heating, cooling to room temperature, pouring into 10 mL water, extracting with chloroform for 3 times, 50mL each time, merging organic phases, washing the organic phases with water for 3 times, 20mL each time, drying with 17.6g anhydrous sodium sulfate, drying with an organic phase by a rotary evaporator, separating with silica gel as a stationary phase by a column chromatography method, eluting with methylene dichloride: methanol=30 mL:1mL, carrying out thin-layer tracking collection on an eluent of a target compound, and carrying out rotary evaporation on the eluent to obtain a dark yellow solid, thus obtaining the heptatomic melon-trimeric indene derivative.
The application of the organic soluble seven-membered cucurbituril-trimeric indene derivative can be used for preparing a high-performance capillary gas chromatographic column.
Compared with the prior art, the invention has the following beneficial effects:
1. The seven-membered cucurbituril-trimeric indene derivative which can be dissolved in an organic solvent is synthesized, has good organic solubility, can be dissolved in organic solvents such as dichloromethane and chloroform, and changes the bottleneck that cucurbituril cannot be dissolved in the organic solvent.
2. According to the invention, the synthesized seven-membered cucurbituril-trimeric indene derivative is used as a stationary phase, and a high-performance capillary gas chromatographic column is prepared by a static coating method, so that xylene isomers and aromatic amine isomer compounds which are difficult to separate can be effectively separated, and the separation performance is better than that of a commercial chromatographic column HP-5. The column efficiency of the chromatographic column is as high as 7860 n/m, and the chromatographic column can be used for separating isomer compounds which are difficult to separate by conventional capillary commodity columns.
Description of the drawings:
fig. 1: a synthetic route of the trimeric indene;
fig. 2: synthetic routes of 5,5 ', 10 ', 15 ' -hexahexyltrimeric indene;
fig. 3: synthetic routes of 2-iodo-5, 5 ', 10 ', 15 ' -hexahexyltrioxyindene;
fig. 4: a synthetic route of the 4-vinylbenzyloxy heptatomic melon ring;
fig. 5: a synthetic route to cucurbituril-trimeric indene derivatives; a step of
Fig. 6: chromatographic separation diagram of chloroaniline isomer (left diagram is chromatographic separation diagram of self-made chromatographic column Q7-T, right diagram is chromatographic separation diagram of commercial chromatographic column HP-5, chromatographic peak 1:2-chloroaniline, chromatographic peak 2:3-chloroaniline, chromatographic peak 3:4-chloroaniline);
Fig. 7: chromatographic separation diagram of diaminodiphenyl methane isomerism (left panel is self-made chromatographic column Q7]-chromatographic separation profile of T, right-hand profile of commercial chromatographic column HP-5, chromatographic peak 1:4,4 ， Diaminodiphenylmethane, chromatographic peak 2:3,3 ， -diaminodiphenyl methane);
fig. 8: chromatographic separation diagram of methylaniline isomer (left diagram is chromatographic separation diagram of self-made chromatographic column Q7-T, right diagram is chromatographic separation diagram of commercial chromatographic column HP-5, chromatographic peak 1: o-methylaniline, chromatographic peak 2: p-methylaniline, chromatographic peak 3: m-methylaniline);
fig. 9: chromatographic separation diagram of diaminotoluene isomer (left diagram is chromatographic separation diagram of self-made chromatographic column Q7-T, right diagram is chromatographic separation diagram of commercial chromatographic column HP-5, chromatographic peak 1:3, 4-diaminotoluene, chromatographic peak 2:2, 3-diaminotoluene, chromatographic peak 3:2, 4-diaminotoluene, chromatographic peak 4:2, 6-diaminotoluene);
fig. 10: chromatographic separation of diaminodiphenyl ether isomer (left panel is self-made chromatographic column Q7]-chromatographic separation profile of T, right-hand profile of commercial chromatographic column HP-5, chromatographic peak 1:4,4 ， Diaminodiphenyl ether, chromatographic peak 2:3,4 ， -diaminophenyl ether);
fig. 11: chromatographic separation patterns of naphthylamine isomers (left panel is chromatographic separation pattern of self-made chromatographic column Q7-T, right panel is chromatographic separation pattern of commercial chromatographic column HP-5, chromatographic peak 1:1-naphthylamine, chromatographic peak 2:2-naphthylamine);
Fig. 12: chromatographic separation diagram of methoxyaniline isomer (left diagram is chromatographic separation diagram of self-made chromatographic column Q7-T, right diagram is chromatographic separation diagram of commercial chromatographic column HP-5, chromatographic peak 1:2-methoxyaniline, chromatographic peak 2:4-methoxyaniline, chromatographic peak 3:3-methoxyaniline);
fig. 13: chromatographic separation diagram of aminobiphenyl isomer (left diagram is chromatographic separation diagram of self-made chromatographic column Q7-T, right diagram is chromatographic separation diagram of commercial chromatographic column HP-5, chromatographic peak 1:2-aminobiphenyl, chromatographic peak 2:3-aminobiphenyl, chromatographic peak 3:4-aminobiphenyl);
fig. 14: chromatographic separation diagram of xylene isomer (left diagram is chromatographic separation diagram of self-made chromatographic column Q7-T, right diagram is chromatographic separation diagram of commercial chromatographic column HP-5, chromatographic peak 1: para-xylene, chromatographic peak 2: meta-xylene, chromatographic peak 3: ortho-xylene).
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1: the synthesis method of the 4-vinylbenzyloxy seven-membered cucurbituril comprises the following steps:
500mg of monohydroxy seven-membered cucurbituril is stirred and dispersed in 7.5mL of anhydrous N, N-dimethylformamide in a 100mL two-neck flask, then 37.5mL of anhydrous dimethyl sulfoxide is added, stirring is continued until the monohydroxy seven-membered cucurbituril is dissolved, the reaction is cooled to 0 ℃ under the protection of N2, naH 850mg is added, stirring is carried out for 4 hours, 1550 mu L of 4-vinylbenzyl chloride is added, ice bath is removed, room temperature is restored for 16 hours, 50mL of diethyl ether is added to precipitate a reaction solution, the obtained precipitate is repeatedly filtered and washed for 3 times by 10mL of methanol, and finally a pale yellow solid is obtained, namely the 4-vinylbenzyloxy seven-membered cucurbituril.
Detection result: the molecular formula of the 4-vinylbenzyloxy seven-membered melon ring is C 51 H 50 N 28 O 15 ， 1 H NMR（D 2 O，400MHz，ppm) δ7.841(s，2H)，δ7.480（d，2H），δ7.361（d，2H），δ6.729（m，1H），δ5.751（d，1H)，δ5.676（br m 12H），δ5.516(br m，14H)，δ5.237（d，1H），4.468（d，2H），δ4.239（m，12H）
Example 2: the synthesis method of 2-iodo-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene comprises the following steps:
(1) Accurately weighing 20.0g of 1-indenone, adding the 1-indenone into 120mL of a mixed solution of glacial acetic acid and 60mL concentrated hydrochloric acid, dissolving, placing the mixed solution in a constant-temperature oil bath pot, slowly heating to 120 ℃, keeping the temperature to reflux for 24 h, rapidly pouring the mixed solution into 1L of ice-water mixture while hot, rapidly stirring while pouring the mixed solution, adding 13.5g of anhydrous sodium carbonate into the solution after uniform distribution, neutralizing unreacted acid, stirring while adding, testing the solution to be neutral by using pH test paper, standing for one hour, precipitating yellow precipitate, repeatedly washing the precipitated yellow precipitate with secondary water for 3 times after decompression and suction filtration, repeatedly washing the precipitate with acetone and dichloromethane for each time until the precipitate is light yellow, and drying to obtain the trimeric indene;
(2) 0.732g of trioxane and 12mL of anhydrous tetrahydrofuran are added into a 50-mL two-neck round-bottom flask, the two-neck round-bottom flask is placed into an ice-water mixture under the protection of nitrogen gas for stirring, after the temperature in the flask is reduced to 0 ℃, 5mL of n-butyllithium is slowly dripped into the flask and reacts for 1.5h at the temperature of 0 ℃, then 1.2mL of 1-bromohexane is slowly dripped into the flask, room temperature is reacted for 4h, the system temperature is reduced to 0 ℃, 5mL of n-butyllithium is slowly dripped into the flask and reacts for 1.5h at the temperature of 0 ℃, then 1.2mL of 1-bromohexane is slowly dripped into the flask, after the room temperature is reacted for 12h, the B product is quenched by 60mL of ammonium chloride saturated solution, the three-dimensional mixture is extracted by methylene chloride for 3 times, 50mL each time, the organic phases are combined, 15g of anhydrous sodium sulfate is added, the organic phase is dried, filtration is carried out, a rotary evaporator is concentrated to 1.2mL at the temperature, 1.4g of silica gel is added, after the silica gel is fully adsorbed, the silica gel is dried on a water bath pot at the temperature of 60 ℃ and is dried, and taken as a sample for column chromatography. Separating the treated sample by using 150-300 mesh silica gel as a stationary phase and petroleum ether as a leaching solution, collecting eluent containing target components 5,5 ', 10', 15 '-hexahexyl trimeric indene confirmed by thin layer chromatography in the separation process, collecting the eluent, spin-drying the solvent of the eluent by a rotary evaporator, and vacuum-drying to obtain bright yellow solid, namely 5, 5', 10 ', 15' -hexahexyl trimeric indene;
(3) Dissolving 1g of 5,5 ', 10 ', 15 ' -hexahexyl trimeric indene in 10mL of dichloromethane, slowly dripping 0.25mL of concentrated nitric acid at 0 ℃ for 2h, carrying out ice-water quenching reaction, extracting twice with dichloromethane, 50mL each time, merging organic phases, washing the organic phases with 60mL of saturated sodium chloride solution, drying the organic phases with 15g of anhydrous sodium sulfate, filtering, spin-drying filtrate with a rotary evaporator, taking 200-mesh silica gel as a stationary phase, and carrying out column chromatography separation on a mixed solution of petroleum ether, dichloromethane=5 mL and 1mL to obtain yellow solid, namely nitrotrimeric indene;
(4) Taking 0.73g of nitrotrimeric indene, 0.46g of iron powder and NH 4 CI 4 Dissolving 0.4g of the crude product in 10mL of 99.7% ethanol, heating and refluxing for reaction for 4 hours at 80 ℃, filtering off solid residues after reaction cooling, spinning the filtrate by a rotary evaporator, dissolving the filtrate by ethyl acetate for 3 times, each time 40 and mL, combining the ethyl acetate solutions, washing the ethyl acetate solutions by 80 and mL saturated sodium chloride solution, drying the ethyl acetate solutions by 12 g of anhydrous sodium sulfate, spinning the ethyl acetate solutions by a rotary evaporator to obtain an initial product, separating 1.21g of the initial product on a 200-300-mesh silica gel column, eluting by petroleum ether of dichloromethane=2 mL/1 mL, tracking target component amino-trimeric indene by thin layer chromatography, and collecting corresponding eluent to obtain the target compound amino-trimeric indene;
(5) Dissolving aminotriazine 0.4. 0.4 g in 1.8mL of dichloromethane, adding 1.2g of silica gel, spin-drying in a rotary evaporator to obtain powder, dissolving the powder in 6mL of water, freezing to 0 ℃, adding 6mL of concentrated hydrochloric acid, stirring vigorously, adding 2.5mL of aqueous solution of 0.9 mmol of sodium nitrite, reacting at 0 ℃ for 1h, adding 3mL of aqueous solution of 1.87 mmol of potassium iodide, reacting for 12h, adding 20mL of saturated sodium bisulfite after the reaction is finished, quenching, adding 70mL of dichloromethane, extracting for 1 time, collecting an organic phase, drying with 7.5g of anhydrous sodium sulfate, spin-drying, separating by using a 200-300 mesh silica gel column as a stationary phase, performing column chromatography, collecting eluent which is petroleum ether in a thin layer trace manner, and spin-drying the eluent by the rotary evaporator to obtain light pink solid, namely 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene.
Detection result: the molecular formula of the 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene is C 63 H 89 I， 1 H NMR(CDCl 3 ，400MHz，ppm) δ7.85（m，11H），δ2.92（m，6H），δ2.03（m，6H），0.67(m，66H)
Example 3: the synthesis method of the seven-membered cucurbituril-trimeric indene derivative comprises the following steps:
adding 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene 80 mg, 4-vinylbenzyloxy heptatomic melon ring 336 mg, anhydrous N, N-dimethylformamide 5mL, triethylamine 1.5mL, palladium acetate 4 mg and 12mg of tris (4-methoxyphenyl) phosphine into a 25mL three-neck flask in an anhydrous anaerobic system, stirring and heating to 85 ℃ to react for 18 hours, stopping heating, cooling to room temperature, pouring into 10 mL water, extracting with chloroform for 3 times, 50mL each time, merging organic phases, washing the organic phases with water for 3 times, 20mL each time, drying with 17.6g anhydrous sodium sulfate, drying with an organic phase by a rotary evaporator, separating with silica gel as a stationary phase by a column chromatography method, eluting with methylene dichloride: methanol=30 mL:1mL, carrying out thin-layer tracking collection on an eluent of a target compound, and carrying out rotary evaporation on the eluent to obtain a dark yellow solid, thus obtaining the heptatomic melon-trimeric indene derivative.
Detection result: seven-membered cucurbituril-trimeric indene derivative with molecular formula of C 114 H 138 N 28 O 15 ， 1 H NMR(CDCl3，400MHz，ppm) δ8.31（d，1H），δ8.17（d，3H）δ7.70(m，1H)，δ7.54（m，11H），δ5.32（m，4H），δ4.40（d，1H），δ4.23（m，4H)，δ2.93（m，6H)，δ2.08（m，6H)，δ0.73（m，66H），ESI-MS m/z:[C 114 H 138 N 28 O 15 +Na] + = 2162.0776 (theoretical calculation 2162.0789).
In order to verify the beneficial effects of the invention, the inventor performs a great deal of experimental study, and the experimental process and the results are as follows:
1. synthesis of seven-membered cucurbituril-trimeric indene star-shaped functional molecule
1. Synthesis of trimeric indene
The trimeric indene is prepared from 1-indenone through multiple aldol condensation and dehydration reactions. Accurately weighing 1-indenone (20.0 g,151 mmol), adding the 1-indenone into a mixed solution of glacial acetic acid (120 mL) and concentrated hydrochloric acid (60 mL), dissolving, placing the mixed solution in a constant-temperature oil bath pot, slowly heating to 120 ℃, keeping the temperature at reflux 24 h, rapidly pouring the reaction product into a 1L ice-water mixture while rapidly stirring while the reaction is hot after the reaction is finished, adding 13.5g of anhydrous sodium carbonate into the solution to neutralize unreacted acid completely after the crude product is uniformly distributed, stirring while adding, and standing for one hour after the solution is neutral by using pH test paper. The yellow precipitate is filtered under reduced pressure, repeatedly washed with secondary water for 3 times (50 per time mL), repeatedly washed with acetone and dichloromethane until the precipitate is light yellow, and dried to obtain the trimeric indene. The synthetic route of the trimeric indene is shown in figure 1.
Synthesis of hexahexyl trimeric indene
0.732 g (2.14 mmol) of indane and 12 mL of anhydrous tetrahydrofuran are placed in a 50mL two-neck round bottom flask and stirred in an ice-water mixture under nitrogen. After the temperature in the flask was lowered to 0 ℃, 5. 5 mL (7.25 mmol 1.6M in hexane) of n-butyllithium was slowly added dropwise to the flask, and reacted at 0 ℃ for 1.5. 1.5 h. 1.2mL (8.43 mmol) of 1-bromohexane was then slowly dropped to react with 4. 4 h at room temperature, the system temperature was then lowered to 0℃and 5 mL (7.25 mmol 1.6M in hexane) of n-butyllithium was slowly dropped into the flask to react with 1.5 h at 0℃and then 1.2mL (8.43 mmol) of 1-bromohexane was slowly dropped to react with 12 h at room temperature. The resultant was quenched with 60mL of saturated ammonium chloride solution, extracted three times with methylene chloride (50 mL. Times.3), the organic phases were combined, dried over 15g of anhydrous sodium sulfate, and the solid was removed by filtration to give an organic solution. Concentrating the organic solvent to 1.2mL, adding 1.4g of silica gel, stirring and loading, fully adsorbing the silica gel, drying the silica gel on a water bath kettle at 60 ℃ and taking the silica gel as a sample for column chromatography loading, taking 150-300 meshes of silica gel as a stationary phase, taking petroleum ether as eluent to separate the treated sample, collecting eluent containing target components confirmed by thin layer chromatography in the separation process, collecting the eluent, spin-drying the solvent of the eluent by a rotary evaporator, and then drying in vacuum to obtain the bright yellow solid of 5,5 ', 10 ', 15 ' -hexahexyl trimeric indene. The synthetic route is shown in FIG. 2.
Synthesis of iodo-5, 5 ', 10 ', 15 ' -hexahexyltrioxyindene
1g (1.18 mmol) of 5,5 ', 10 ', 15 ' -hexahexyltrimeric indene is taken and dissolved in dichloromethane (10 mL) at 00.25 mL concentrated nitric acid was slowly added dropwise at c, reaction 2 h, quenched with ice water, extracted with dichloromethane twice (50 mL x 2), the organic phases were combined, washed with 60mL saturated sodium chloride solution, dried over 15g anhydrous sodium sulfate, spun-dried, separated by column chromatography, and the eluent was petroleum ether dichloromethane=5:1 (v/v) to give nitroindane yellow solid. Nitrotrimeric indene 0.73g (0.82 mmol), iron powder 0.46g (8.2 mmol), NH 4 CI 4 0.4g (8.2 mmol) of the crude product was dissolved in 10 mL of 99.7% ethanol and reacted for 4 hours under reflux, the solid residue was filtered off after cooling the reaction, and the filtrate was dried by spin-drying and then dissolved in ethyl acetate, extracted, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate and dried by spin-drying to obtain the crude product. Separating 1.21g of the initial product on a silica gel column (200-300 mesh silica gel), wherein the eluent is petroleum ether, dichloromethane=2:1 (v/v), tracking the target component by thin layer chromatography, and collecting the corresponding eluent to obtain the target compound, namely the amino-trimeric indene. Aminotrioxyindene 0.4g (0.465 mmol) was dissolved in 1.8mL of dichloromethane, followed by addition of silica gel 1.2 g and spin-drying to a powder on a rotary evaporator. The powder was dissolved in 6mL water and frozen to 0℃and 6mL of concentrated hydrochloric acid was added with vigorous stirring, followed by addition of 66mg (0.90 mmol) of sodium nitrite in water (2.5 mL), and the mixture was reacted at 0℃for 1 hour, followed by addition of 0.31g (1.87 mmol) of potassium iodide in water (3 mL) and the reaction was continued overnight. After the reaction is finished, the reaction is quenched by 20mL of saturated sodium bisulfite, 70mL of dichloromethane is used for extraction for 1 time, 7.5g of anhydrous sodium sulfate is used for drying an organic phase, after the organic phase is dried in a spinning way, a silica gel column (200-300 meshes of silica gel) column chromatography is used for separation, eluent is petroleum ether, the eluent of a target compound is collected by thin-layer tracking, and 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene light pink solid is obtained after the eluent is dried in a spinning evaporator. C (C) 63 H 89 I， 1 H NMR(CDCl 3 400mhz, ppm) delta 7.85 (m, 11H), delta 2.92 (m, 6H), delta 2.03 (m, 6H), 0.67 (m, 66H). The synthetic route is shown in FIG. 3.
Synthesis of vinylbenzyloxy heptatomic melon ring
In a two-necked flask of 100 mL, 500 mg (0.42 mmol) of a monohydroxy seven-membered ring was dispersed in 7.5 mL anhydrous N, N-dimethylformamide with stirring, and then 37.5 mL anhydrous dimethyl sulfoxide was added to the suspension. Stirring is continued until monohydroxyDissolving seven-membered melon ring in N 2 The reaction was cooled to 0deg.C with protection, 850 mg (35.42 mmol) NaH was added and the reaction was stirred 4 h. 1550 μl (10.94 mmol) of 4-vinylbenzyl chloride was then added to the reaction mixture and the ice bath was removed to restore room temperature reaction 16 h. And (3) adding 50mL of diethyl ether to precipitate the reaction solution after the reaction, repeatedly filtering and washing the obtained precipitate with 10 mL methanol for 3 times, and finally obtaining a light yellow 4-vinylbenzyloxy seven-membered cucurbituril solid. C (C) 51 H 50 N 28 O 15 ， 1 H NMR（D 2 O,400MHz, ppm) delta 7.841 (s, 2H), delta 7.480 (d, 2H), delta 7.361 (d, 2H), delta 6.729 (m, 1H), delta 5.751 (d, 1H), delta 5.676 (br m 12H), delta 5.516 (br m, 14H), delta 5.237 (d, 1H), 4.468 (d, 2H), delta 4.239 (m, 12H). The synthetic route is shown in FIG. 4.
Synthesis of seven-membered cucurbituril-trimeric indene star-shaped molecule
Into a 25 mL three-necked flask, 80 mg (0.082 mmol) of 2-iodo-5, 5 ', 10 ', 15 ' -hexahexyltrione, 336 mg (0.26 mmol) of 4-vinylbenzyloxy seven-membered melon ring, 5 mL anhydrous N, N-dimethylformamide, 1.5 mL triethylamine, 4mg palladium acetate and 12mg of tris (4-methoxyphenylphosphine) were charged in an anhydrous and anaerobic system as a catalyst, and the mixture was stirred and heated to 85℃to react for 18 hours. The heating was stopped, the reaction mixture was poured into 10. 10mL water, extracted three times with chloroform (50 mL. Times.3), and the organic phase was washed three times with water (20 mL. Times.3) and dried over 17.6g of anhydrous sodium sulfate. The organic phase is separated by a silica gel column chromatography after spin-drying by a rotary evaporator, the eluent is dichloromethane, methanol=30:1 (v/v), the eluent of the target compound is collected by thin-layer tracking, and the eluent is spin-dried by the rotary evaporator to obtain the deep yellow solid heptatomic cucurbituril-trioxyindene derivative. C (C) 114 H 138 N 28 O 15 ， 1 H NMR(CDCl3，400MHz，ppm) δ8.31（d，1H），δ8.17（d，3H）δ7.70(m，1H)，δ7.54（m，11H），δ5.32（m，4H），δ4.40（d，1H），δ4.23（m，4H)，δ2.93（m，6H)，δ2.08（m，6H)，δ0.73（m，66H），ESI-MS m/z:[C 114 H 138 N 28 O 15 +Na] + = 2162.0776 (theoretical calculation 2162.0789). The synthetic circuit is shown in the figure5。
2. Determination of solubility of seven-membered guacyclo-trimeric indene derivatives (Q7-Tr)
Six solvents were chosen to determine the solubility of Q7-Tr, two of which were each of the weak, medium and strong polarity solvents. Accurately weighing excess Q7-Tr, loading into a dry three-neck flask, adding 10mL of petroleum ether, inserting a thermometer at one port, and connecting a condenser tube at one port. The flask was placed in a magnetic stirring heating pot, stirring was started, the temperature was raised to 25 ℃, stirring was performed at constant temperature for 1h, then the supernatant and undissolved solids were centrifuged (5000 r/min), and the mass of the dried solids was accurately weighed out with an analytical balance. Repeating the dissolution experiment (the stirring time length is changed to 1.5h, other steps are unchanged), measuring the dissolved solid mass difference of less than 0.4mg twice, taking the average value of the two measurements, and continuing to prolong the stirring time length until the two mass differences are consistent with the requirements. The solubility of Q7-Tr in other solvents was determined in the same manner at 25 ℃. The measurement results are shown in Table 1. The results show that Q7-Tr has better solubility in methylene chloride, chloroform and N, N-dimethylformamide.
TABLE 1 solubility of Q7-Tr in six solvents
Solvent(s) Petroleum ether N-hexane Dichloromethane (dichloromethane) Trichloromethane N, N-dimethylformamide Methanol
Solubility/[ mol.L ] -1 ] 3.38×10 -5 3.55×10 -5 1.37×10 -3 1.77×10 -3 1.08×10 -3 9.17×10 -5
3. Preparation and performance measurement of seven-membered cucurbituril-trimeric indene derivative capillary gas chromatographic column
Instrument: gas chromatograph GC-2014C (Shimadzu Japan)
Chromatographic test conditions: sample inlet: 270 ℃; FID detector: 280 ℃; split sample injection (50:1); carrier gas: high-purity nitrogen; carrier gas flow rate: 1mL/min; sample injection amount: 0.4. Mu.L.
1. Preparation of seven-membered cucurbituril-trimeric indene derivative (Q7-Tr) capillary gas chromatographic column
Pretreatment of a capillary column: a quartz capillary column with the inner diameter of 10 m and the inner diameter of 0.25 mm is taken, and is continuously washed for 20 min by dichloromethane, and aged for 3h at 260 ℃ under the protection of nitrogen. 1.31g of NaCl is weighed and dissolved in 10 mL absolute methanol, and is strongly stirred for 45 min, supernatant 6 mL is taken and added into 8mL of chloroform solution which is strongly stirred, 0.6 mL methanol is added and stirred for 5min, and 8mL chloroform is added and stirred for 2 min, so that a NaCl saturated solution is obtained. And (3) allowing the NaCl solution to pass through the capillary column under proper pressure, observing the liquid flowing out of the capillary column, stopping when the turbidity of the effluent is equivalent to that of the original saturated solution, discharging the solution in the column completely, and aging for 3 hours at 200 ℃ under nitrogen purging.
Stationary phase coating, namely coating the stationary phase by adopting a static method. 20 mg of Q7-Tr was dissolved in 10mL of methylene chloride solution to prepare a solution having a concentration of 0.20% (w/v), and the solution was subjected to ultrasonic deaeration for 5 minutes. One end of the capillary column is connected with a vacuum bottle (vacuumized to 0.08 MPa), the other end of the capillary column is inserted below the liquid level of the fixed liquid, and the vacuum bottle is closed after the capillary column is filled with the solution. One end inserted into the fixing liquid is quickly pulled out and is blocked by a rubber plug, the other end is connected with vacuum, and the solvent is slowly and completely volatilized in a constant-temperature water bath at 39 ℃ to finish the column preparation.
Aging of the chromatographic column: one end of the chromatographic column coated with the stationary phase is connected with a gas chromatograph sample inlet, aged in a temperature programming mode under the protection of nitrogen, the initial temperature is 40 ℃, the temperature is increased to 150 ℃ at 2 ℃/min and kept for 180 min, and the temperature is increased to 240 ℃ at 2 ℃/min and kept for 240 min. Thus, the preparation of the Q7-Tr chromatographic column is completed.
2. Determination of column effect and polarity of chromatographic column
Dodecane is used as a test sample, the maximum column effect of the Q7-Tr chromatographic column is 7860n/m, the average polarity of the chromatographic column is 65, and the prepared chromatographic column belongs to a weak polarity column and has similar polarity with the commercial chromatographic column HP-5.
4. Separation of organic isomer compounds
The isomers have similar structures and similar boiling points, so that the separation performance of the capillary gas chromatographic column can be best shown by the separation of the isomers. The separation of 22 aromatic amine isomers was performed on the prepared Q7-Tr column and compared with the separation results of commercial column HP-5.
Separation of (mono) chloroaniline isomers
The separation conditions are (1) Q7-Tr 160 ℃ (1 min) 3 ℃/min 210 ℃ (1 min), (2) HP-5:160 ℃ (1 min) 3 ℃/min 210 ℃ (1 min).
As can be seen from FIG. 6, the separation of the three isomers by the self-made chromatographic column Q7-Tr (left panel) is good, whereas the commercial chromatographic column HP-5 (right panel) is not capable of separating 3-chloroaniline from 4-chloroaniline.
(di) diaminodiphenyl methane isomer
The separation conditions are (1) Q7-Tr 180 ℃ (1 min) 5 ℃/min 250 (2 min), (2) HP-5:180 ℃ (1 min) 3 ℃/min 240 (1 min).
As can be seen from FIG. 7, both column pairs of diaminodiphenyl methane isomers can be separated, but the separation effect of the self-made column Q ] 7-Tr (left panel) is better than that of the commercial column HP-5 (right panel).
(tri) methylaniline isomers
Separation conditions: (1) Q7-Tr separation conditions: 90 ℃ (1 min) 4 ℃/min 130 ℃ (1 min), (2) HP-5 separation conditions 80 ℃ (1 min) 5 ℃/min140 ℃ (1 min).
As can be seen from FIG. 8, neither the self-made column Q ] 7-Tr (left panel) nor the commercial column HP-5 (right panel) was able to separate para-methylaniline from para-methylaniline.
(IV) diaminotoluene isomers
The separation conditions are (1) Q7-Tr 100 ℃ (1 min) 8 ℃/min 250 ℃ (6 min), (2) HP-5:110 ℃ (1 min) 8 ℃/min 250 ℃ (3 min).
As can be seen from FIG. 9, the self-made chromatographic column Q7-Tr (left panel) has better separation for all four diaminotoluene isomers, whereas the commercial chromatographic column HP-5 (right panel) has no separation for both 2, 4-diaminotoluene and 2, 6-diaminotoluene isomers.
(five) diaminodiphenyl ether isomer
The separation conditions are (1) Q7-Tr 170 ℃ (1 min) 6 ℃/min 260 ℃ (6 min), (2) HP-5:170 ℃ (1 min) 6 ℃/min 260 ℃ (6 min).
As can be seen from FIG. 10, both column isomers of p-diaminodiphenyl ether can be separated, but the separation effect of the self-made column Q ] 7-Tr (left panel) is better than that of the commercial column HP-5 (right panel).
Naphthylamine isomer (six)
Separation conditions: (1) Q7-Tr, 3 ℃/min 200 ℃ (1 min) (2) HP-5:160 ℃ (1 min) 3 ℃/min 200 (1 min).
As can be seen from FIG. 11, both columns (Q ] 7-Tr (left panel) and commercial column HP-5 (right panel) are capable of separating the naphthylamine isomers.
(hepta) methoxy aniline isomer
Separation conditions: (1) Q7-Tr 140 (1 min) 5 ℃/min 200 (1 min), (2) HP-5:160 ℃ (1 min) 5 ℃/min 200 ℃ (1 min).
As can be seen from FIG. 12, both columns (Q ] 7-Tr (left panel) and commercial column HP-5 (right panel) para-methoxyaniline isomers can be separated.
(eight) aminobiphenyl isomers
Separation conditions: (1) Q7-Tr, 6deg.C/min 250 (4 min) at 150deg.C; (2) HP-5:160 ℃ (1 min) 8 ℃/min 250 ℃ (4 min).
As can be seen from FIG. 13, the self-made column (Q ] 7-Tr (left panel) was able to separate for all three of the aminobiphenyl isomers, whereas the commercial column HP-5 (right panel) was completely unable to separate for both 3-aminobiphenyl and 4-aminobiphenyl isomers.
Xylene isomer (nine)
Separation conditions: (1) Q7-Tr 65 ℃ (15 min), 0.6mL/min, (2) HP-5:60 ℃ (15 min), 0.6mL/min.
As can be seen from FIG. 14, the homemade column (Q ] 7-Tr (left panel) was able to separate all three xylene isomers, whereas the commercial column HP-5 (right panel) was completely unable to separate both para-xylene and para-xylene isomers.
TABLE 2 separation parameters of chromatographic column versus positional isomers
Note that: k is a retention factor, alpha is a separation factor, and R is a separation degree
From FIGS. 8, 9 and Table 2, it can be seen that the self-made chromatographic column Q7-Tr has good separation effect on other 7-class positional isomers except that the self-made chromatographic column Q7-Tr cannot separate p-methylaniline from o-methylaniline and the self-made chromatographic column Q4-Tr cannot completely separate 2, 6-diaminotoluene from 2, 6-diaminotoluene. The separation effect of five isomers of the p-chloroaniline, the diaminotoluene, the aminobiphenyl, the xylene and the diaminodiphenyl ether of the commercial chromatographic column HP-5 is poor, which shows that the separation performance of the self-made chromatographic column is superior to that of the commercial column HP-5.

Claims (7)

1. A first partAn organic soluble seven-membered cucurbituril-trimeric indene derivative which is characterized in that: the molecular formula of the seven-membered cucurbituril-trimeric indene derivative is C 114 H 138 N 28 O 15 The structural formula is as follows:
。
2. a process for the synthesis of an organic soluble seven membered cucurbituril-trimeric indene derivative as defined in claim 1, characterized in that: the seven-membered cucurbituril-trioxyindene derivative is prepared by derivatizing monohydroxy seven-membered cucurbituril into 4-vinylbenzyloxy seven-membered cucurbituril, derivatizing trioxyindene into 2-iodo-5, 5', 10',15 '-hexahexyl trioxyindene, and synthesizing the 4-vinylbenzyloxy seven-membered cucurbituril and the 2-iodo-5, 5',10 ', 15' -hexahexyl trioxyindene into the seven-membered cucurbituril-trioxyindene derivative through substitution reaction;
The synthesis method of the 4-vinylbenzyloxy seven-membered cucurbituril specifically comprises the following steps: dispersing monohydroxy seven-membered cucurbituril in anhydrous N, N-dimethylformamide under stirring in a two-neck flask, adding anhydrous dimethyl sulfoxide, stirring continuously until the monohydroxy seven-membered cucurbituril is dissolved, and adding the mixture into N 2 Cooling the reaction to 0 ℃ under protection, adding NaH, stirring to react for 3-5 h, adding 4-vinylbenzyl chloride, removing ice bath to restore room temperature to react for 14-18 h, adding diethyl ether to precipitate reaction liquid, repeatedly filtering and washing the obtained precipitate with methanol for 2-4 times, and finally obtaining light yellow solid, namely obtaining the 4-vinylbenzyloxy seven-membered melon ring;
the synthesis method of the 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene specifically comprises the following steps:
(1) Accurately weighing 1-indenone, adding the 1-indenone into a mixed solution of glacial acetic acid and concentrated hydrochloric acid, dissolving the mixture, then placing the mixture in a constant-temperature oil bath pot, slowly heating the mixture to 110-130 ℃, keeping the temperature to reflux for 22-26 hours, rapidly pouring the mixture into an ice-water mixture while hot, rapidly stirring the mixture while pouring the mixture into the mixture, adding anhydrous sodium carbonate into the solution after uniform distribution, neutralizing unreacted acid, stirring the mixture while adding, testing the solution to be neutral by using pH test paper, standing for one hour, separating out yellow precipitate, performing vacuum filtration on the separated yellow precipitate, repeatedly washing the yellow precipitate by using secondary water for 2-4 times, repeatedly washing the precipitate by using acetone and dichloromethane each time until the precipitate is light yellow, and drying the precipitate to obtain the indene;
(2) Adding trioxane and anhydrous tetrahydrofuran into a 50mL two-neck round bottom flask, stirring in an ice-water mixture under the protection of nitrogen, slowly dripping n-butyllithium into the flask when the temperature in the flask is reduced to 0 ℃, reacting at 0 ℃, slowly dripping 1-bromohexane, reacting at room temperature for 3-5h, reducing the system temperature to 0 ℃, slowly dripping n-butyllithium into the flask, reacting at 0 ℃ for 1-2 h, slowly dripping 1-bromohexane, reacting at room temperature for 10-14h, quenching with an ammonium chloride saturated solution, extracting with dichloromethane three times, 40-60mL each time, combining organic phases, adding anhydrous sodium sulfate, drying the organic phases, filtering, concentrating to 1.2 mL at 40 ℃ by a rotary evaporator, adding 1.4g of silica gel, fully adsorbing the silica gel, drying the silica gel on a water bath kettle at 60 ℃ and taking the silica gel as a sample for column chromatography, taking 150-300 meshes of silica gel as a stationary phase, taking petroleum ether as eluent to separate the treated sample, collecting eluent containing target components 5,5 ', 10', 15 '-hexahexyl trimeric indene confirmed by thin layer chromatography in the separation process, collecting the eluent, spin-drying the solvent by the rotary evaporator, and then vacuum drying to obtain bright yellow solid, namely 5, 5', 10 ', 15' -hexahexyl trimeric indene;
(3) Dissolving 5,5 ', 10 ', 15 ' -hexahexyl trimeric indene in dichloromethane, slowly dropwise adding concentrated nitric acid at 0 ℃ for reaction for 1-3h, carrying out ice-water quenching reaction, extracting twice with dichloromethane, 40-60mL each time, combining organic phases, washing the organic phases with 50-70mL saturated sodium chloride solution, drying the organic phases with anhydrous sodium sulfate, filtering, spin-drying the filtrate with a rotary evaporator, taking 200-mesh silica gel as a stationary phase, and separating the eluent with petroleum ether of dichloromethane=5 mL/1 mL mixed solution by column chromatography to obtain yellow solid, namely nitrotrimeric indene;
(4) Taking nitrotrimeric indene, iron powder and NH 4 CI 4 Dissolving in 99.7% absolute ethanol, heating and refluxing at 80deg.C3-5h, filtering out solid residues after reaction cooling, spinning the filtrate by a rotary evaporator, dissolving the filtrate by ethyl acetate for 3 times, 40mL each time, combining ethyl acetate solutions, washing the ethyl acetate solutions by 80mL of saturated sodium chloride solution, drying the ethyl acetate solutions by 12g of anhydrous sodium sulfate, spinning the extract by the rotary evaporator, separating the extract on a 150-350-mesh silica gel column, wherein the eluent is petroleum ether and dichloromethane mixed solution = 2mL:1mL, tracking target components of aminotriazine by thin layer chromatography, and collecting corresponding eluent to obtain aminotriazine;
(5) Dissolving aminotriazine in dichloromethane, adding silica gel into the dichloromethane, spin-drying the solution in a rotary evaporator to obtain powder, dissolving the powder in water, freezing to 0 ℃, adding concentrated hydrochloric acid, stirring vigorously, adding aqueous solution of sodium nitrite, reacting for 0.5-1.5h at 0 ℃, adding aqueous solution of potassium iodide, reacting for 8-14h, adding saturated sodium bisulfite to quench the reaction, adding 70mL of dichloromethane to extract for 1 time, collecting organic phase, drying with anhydrous sodium sulfate, spin-drying, separating by using a 150-350 mesh silica gel column as a stationary phase, separating by a column chromatography method, eluting with petroleum ether, carrying out thin-layer tracking, collecting eluent of a target compound, and spin-drying the eluent by the rotary evaporator to obtain light pink solid, namely 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyltrizole;
the synthesis method of the seven-membered cucurbituril-trimeric indene derivative specifically comprises the following steps: adding 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene, 4-vinylbenzyloxy heptatomic melon ring, anhydrous N, N-dimethylformamide, triethylamine, palladium acetate and tri (4-methoxyphenyl) phosphine into a 25mL three-neck flask in an anhydrous anaerobic system, stirring and heating to 75-95 ℃ to react for 16-20h, stopping heating, cooling to room temperature, pouring into water, extracting with chloroform for 3 times, 40-60mL each time, merging organic phases, washing the organic phases with water for 3 times, 15-25mL each time, drying with anhydrous sodium sulfate, drying the organic phases with a rotary evaporator, separating with a silica gel as a stationary phase by a column chromatography, eluting with dichloromethane: methanol=20-35 mL, carrying out thin-layer tracking and collecting eluent of a target compound, and carrying out rotary evaporation on the eluent to obtain a dark yellow solid, namely the heptatomic melon ring-trimeric indene derivative.
3. The method for synthesizing the organic soluble seven-membered cucurbituril-trimeric indene derivative according to claim 2, which is characterized in that: the synthesis method of the 4-vinylbenzyloxy seven-membered cucurbituril specifically comprises the following steps:
in a two-neck flask of 100 mL, a monohydroxy seven-membered melon ring 500 mg is stirred and dispersed in 7.5mL anhydrous N, N-dimethylformamide, then 37.5mL anhydrous dimethyl sulfoxide is added, and stirring is continued until the monohydroxy seven-membered melon ring is dissolved, and the mixture is stirred and dispersed in N 2 Cooling the reaction to 0 ℃ under protection, adding NaH 850 mg, stirring to react for 4 h, adding 1550 mu L of 4-vinylbenzyl chloride, removing ice bath to restore room temperature to react for 16 h, adding 50 mL diethyl ether to precipitate reaction liquid, repeatedly filtering and washing the obtained precipitate with 10 mL methanol for 3 times, and finally obtaining a light yellow solid, namely the 4-vinylbenzyloxy heptatomic melon ring.
4. The method for synthesizing the organic soluble seven-membered cucurbituril-trimeric indene derivative according to claim 2, which is characterized in that: the synthesis method of the 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene specifically comprises the following steps:
(1) Accurately weighing 20.0g of 1-indenone, adding the 1-indenone into a mixed solution of 120 mL glacial acetic acid and 60 mL concentrated hydrochloric acid, dissolving, placing the mixed solution in a constant-temperature oil bath pot, slowly heating to 120 ℃, keeping the temperature to reflux 24 h, rapidly pouring the mixed solution into 1L of ice-water mixture while hot, pouring the mixed solution while rapidly stirring, adding 13.5g of anhydrous sodium carbonate into the solution after uniform distribution, neutralizing the unreacted acid, stirring while adding, testing the solution to be neutral by using pH test paper, standing for one hour, precipitating yellow precipitate, repeatedly washing the precipitated yellow precipitate with secondary water for 3 times after decompression and suction filtration, repeatedly washing the precipitate to be light yellow by using acetone and dichloromethane each time, and drying to obtain the trimeric indene;
(2) Adding 0.732g of trimeric indene and 12mL of anhydrous tetrahydrofuran into a 50mL two-neck round bottom flask, stirring in an ice-water mixture under the protection of nitrogen, slowly dripping 5mL of n-butyllithium into the flask when the temperature in the flask is reduced to 0 ℃, reacting for 1.5h at 0 ℃, slowly dripping 1.2mL of 1-bromohexane, reacting for 4h at room temperature, reducing the system temperature to 0 ℃, slowly dripping 5mL of n-butyllithium into the flask, reacting for 1.5h at 0 ℃, slowly dripping 1.2mL of 1-bromohexane, quenching with 60mL of ammonium chloride saturated solution after reacting for 12h at room temperature, extracting with dichloromethane three times, 50mL each time, combining organic phases, adding 15g of anhydrous sodium sulfate to dry an organic phase, filtering, concentrating to 1.2mL at 40 ℃ by a rotary evaporator, adding 1.4g of silica gel, fully adsorbing the silica gel, drying the silica gel on a water bath kettle at 60 ℃ and taking the silica gel as a sample for column chromatography, taking 150-300 meshes of silica gel as a stationary phase, taking petroleum ether as eluent to separate the treated sample, collecting eluent which is confirmed by thin layer chromatography and contains target components 5,5 ', 10', 15 '-hexahexyl trimeric indene in the separation process, collecting the eluent, spin-drying the solvent by the rotary evaporator, and then carrying out vacuum drying to obtain bright yellow solid, namely 5, 5', 10 ', 15' -hexahexyl trimeric indene;
(3) Dissolving 1g of 5,5 ', 10 ', 15 ' -hexahexyl trimeric indene in 10mL of dichloromethane, slowly dripping 0.25mL of concentrated nitric acid at 0 ℃ for 2h, carrying out ice-water quenching reaction, extracting twice with dichloromethane, 50mL each time, merging organic phases, washing the organic phases with 60mL of saturated sodium chloride solution, drying the organic phases with 15g of anhydrous sodium sulfate, filtering, spin-drying filtrate with a rotary evaporator, taking 200-mesh silica gel as a stationary phase, and carrying out column chromatography separation on a mixed solution of petroleum ether, dichloromethane=5 mL and 1mL to obtain yellow solid, namely nitrotrimeric indene;
(4) Taking 0.73g of nitrotrimeric indene, 0.46g of iron powder and NH 4 CI 4 0.4g of the solid residue is filtered after being dissolved in 10mL of 99.7% ethanol and heated and refluxed at 80 ℃ for 4 hours, the filtrate is dried by spin-drying by a rotary evaporator for 3 times, each time 40 percent mL is dissolved by ethyl acetate, the combined ethyl acetate solution is washed by 80 percent mL saturated sodium chloride solution, then 12 grams of anhydrous sodium sulfate is dried, the solvent is dried by spin-drying by a rotary evaporator, the solvent is separated on a 200-300-mesh silica gel column, the eluent is petroleum ether, dichloromethane=2mL:1mL, the target component amino-trimeric indene is tracked by thin layer chromatography, and the corresponding eluent is collected, so as to obtain the amino-trimeric indene;
(5) Dissolving aminotriazine 0.4. 0.4 g in 1.8mL of dichloromethane, adding 1.2g of silica gel, spin-drying in a rotary evaporator to obtain powder, dissolving the powder in 6mL of water, freezing to 0 ℃, adding 6mL of concentrated hydrochloric acid, stirring vigorously, adding 2.5mL of aqueous solution of 0.9 mmol of sodium nitrite, reacting at 0 ℃ for 1h, adding 3mL of aqueous solution of 1.87 mmol of potassium iodide, reacting for 12h, adding 20mL of saturated sodium bisulfite after the reaction is finished, quenching, adding 70mL of dichloromethane, extracting for 1 time, collecting an organic phase, drying with 7.5g of anhydrous sodium sulfate, spin-drying, separating by using a 200-300 mesh silica gel column as a stationary phase, performing column chromatography, collecting eluent which is petroleum ether in a thin layer trace manner, and spin-drying the eluent by the rotary evaporator to obtain light pink solid, namely 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene.
5. The method for synthesizing the organic soluble seven-membered cucurbituril-trimeric indene derivative according to claim 2, which is characterized in that: the synthesis method of the seven-membered cucurbituril-trimeric indene derivative specifically comprises the following steps:
adding 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene 70-90 mg, 4-vinylbenzyloxy heptatomic melon ring 320-350 mg, anhydrous N, N-dimethylformamide 4-6mL, triethylamine 1-2mL, palladium acetate 3-5mg and 10-14mg of tris (4-methoxyphenyl) phosphine into a 25mL three-neck flask, stirring and heating to 85-90 ℃ for 17-19h, stopping heating, cooling to room temperature, pouring into 10 mL water, extracting with chloroform for 3 times, 45-55 mL each time, merging organic phases, washing the organic phases with water for 3 times, each time with 18-22 mL, drying with 16-20 g anhydrous sodium sulfate, spin-drying the organic phases with a rotary evaporator, separating with silica gel column chromatography, eluting with dichloromethane=30 mL of methanol, 1mL, tracking and collecting eluent of a target compound in a thin layer, spin-drying the eluent with a rotary evaporator to obtain the heptatomic indene derivative.
6. The method for synthesizing the organic soluble seven-membered cucurbituril-trimeric indene derivative according to claim 2, which is characterized in that: the synthesis method of the seven-membered cucurbituril-trimeric indene derivative specifically comprises the following steps:
adding 2-iodine-5, 5 ', 10 ', 15 ' -hexahexyl trimeric indene 80 mg, 4-vinylbenzyloxy heptatomic melon ring 336 mg, anhydrous N, N-dimethylformamide 5mL, triethylamine 1.5mL, palladium acetate 4 mg and 12mg of tris (4-methoxyphenyl) phosphine into a 25mL three-neck flask in an anhydrous anaerobic system, stirring and heating to 85 ℃ to react for 18 hours, stopping heating, cooling to room temperature, pouring into 10 mL water, extracting with chloroform for 3 times, 50mL each time, merging organic phases, washing the organic phases with water for 3 times, 20mL each time, drying with 17.6g anhydrous sodium sulfate, drying with an organic phase by a rotary evaporator, separating with silica gel as a stationary phase by a column chromatography method, eluting with methylene dichloride: methanol=30 mL:1mL, carrying out thin-layer tracking collection on an eluent of a target compound, and carrying out rotary evaporation on the eluent to obtain a dark yellow solid, thus obtaining the heptatomic melon-trimeric indene derivative.
7. Use of an organic soluble seven-membered cucurbituril-triindene derivative according to claim 1, characterized in that: the organic soluble seven-membered cucurbituril-trimeric indene derivative can be used for preparing a capillary gas chromatographic column.
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