An alkyl-functionalized inclined hexaphene for stationary phase, and a preparation method, capillary gas chromatographic column and application thereof

Abstract

The application provides a preparation method of alkyl-functionalized inclined hexaphenyls for fixing phases, which comprises the following steps: step 1, single halogenated hydrocarbon etherification: 1,4-benzenediol is reacted with 1-bromodecane, potassium hydroxide and ethanol by heating, after the reaction, the temperature is reduced, post-treatment is carried out, and purification is carried out to obtain an intermediate (I); step 2, Friedel-Crafts alkylation: the intermediate (I) obtained in step 1, 1,4-p-dichlorobenzyl, aluminum trichloride and dichloromethane are reacted at room temperature, after the reaction, post-treatment is carried out, and purification is carried out to obtain an intermediate (II); step 3, cyclization: the intermediate (II) obtained in step 2, paraformaldehyde, boron trifluoride etherate and dichloromethane are mixed, after the reaction, post-treatment and purification are carried out to obtain an alkyl-functionalized inclined hexaphenyls (III), the alkyl-functionalized inclined hexaphenyls (III) has uniform particle size distribution on a capillary gas chromatography column, and has better separation effect on substituted benzaldehyde isomer compounds and halogenated benzene isomer compounds.

Description

Technical Field

[0001] This invention belongs to the field of chromatographic analysis technology, and particularly relates to an alkyl-functionalized hexaaromatic hydrocarbon for stationary phase, its preparation method, a capillary gas chromatography column and its application. Background Technology

[0002] Chromatography is the most commonly used analytical separation method in modern chemical industry systems. Gas chromatography (GC) is one of the most frequently used chromatographic separation techniques today. Due to its advantages such as high sensitivity, high selectivity, short analysis time, and small sample volume, it has been widely applied in sample separation and analysis across various fields. GC separates components in a sample based on their different physicochemical properties, thereby determining the content of each component in the mixture. It is one of the methods for qualitative and quantitative analysis of complex mixtures. Compared to traditional packed columns, capillary gas chromatography offers significant improvements in separation efficiency and analysis speed.

[0003] In all structures of gas chromatography, the column plays the primary separation function. All separation processes of the sample are completed within the column. The type of stationary phase, coating method, and coating thickness all affect column efficiency, identification sensitivity, and separation performance. The separation effect of the sample is mainly related to the properties of the stationary phase; therefore, the stationary phase coated on the column is crucial to the separation process.

[0004] Some important supramolecular compounds, such as crown ethers, cyclodextrins, calixarenes, cucurbiturils, and columnar aromatics, have been reported in gas chromatography. However, the separation of substituted benzaldehyde isomers, aniline isomers, halobenzene isomers, some cis-trans isomers, and complex mixtures using existing stationary phases remains unsatisfactory. Inclined aromatics, as a novel type of supramolecular compound, possess a unique cyclic molecular structure, and their use as a gas chromatography stationary phase may offer special chromatographic selectivity. Furthermore, alkylation modification can improve the film-forming properties, thermal stability, and chemical stability of inclined aromatics.

[0005] Therefore, in order to solve the above-mentioned technical problems, the present invention provides an alkyl-functionalized hexaaromatic hydrocarbon for the stationary phase, a method for its preparation, a capillary gas chromatography column and its application. Summary of the Invention

[0006] Purpose of the invention:

[0007] In order to overcome the shortcomings and disadvantages of the prior art, the present invention aims to provide an alkyl-functionalized hexaaromatic hydrocarbon for the stationary phase, a method for its preparation, a capillary gas chromatography column and its application, and to provide the application of the above-mentioned capillary gas chromatography column by preparing the capillary gas chromatography column by static coating method.

[0008] Technical solution:

[0009] An alkyl-functionalized hexane for use as a stationary phase, the chemical structural formula of which is:

[0010]

[0011] A method for preparing alkyl-functionalized hexaaromatic hydrocarbons for use as a stationary phase, comprising the following steps:

[0012] Step 1, Monohalogenated hydrocarbon etherification: 1,4-benzenediol was heated to react with 1-bromodecane, potassium hydroxide and ethanol. After the reaction was completed, the mixture was cooled, post-processed and purified to obtain intermediate (Ⅰ).

[0013] Step 2, Friedel-Crafts alkylation: The intermediate (Ⅰ) obtained in Step 1, 1,4-dichlorobenzyl chloride, aluminum trichloride and dichloromethane are reacted at room temperature. After the reaction is completed, post-processing and purification are performed to obtain intermediate (Ⅱ).

[0014] Step 3, Cyclolysis: The intermediate (II) obtained in step 2, paraformaldehyde, boron trifluoride ether and dichloromethane are mixed. After the reaction is completed, DeLP6A(III) is obtained after post-processing and purification. The obtained DeLP6A(III) has a uniform particle size distribution on a capillary gas chromatography column.

[0015] In step 1, the reaction temperature is 80–85°C; the reaction time is 4.5–5.5 h; the temperature is then lowered to 25°C; the molar ratio of 1,4-benzenediol to 1-bromodecane is 1.0:3.0–3.1; the molar ratio of 1,4-benzenediol to potassium hydroxide is 1.0:3.0–3.1; the mass-to-volume ratio of 1,4-benzenediol, 1-bromodecane, potassium hydroxide, and ethanol is 1.0 g:6.0–6.3 g:1.5–1.6 g:22–25 mL; during purification, recrystallization is performed using ethanol as the solvent.

[0016] In step 2, the reaction was carried out at 25°C; the reaction time range was 2–3 h; the molar ratio of 1,4-dichlorobenzyl to intermediate (I) was 1.0:5.0–5.1; the molar ratio of 1,4-dichlorobenzyl to potassium hydroxide was 1.0:3.0–3.1; the mass-to-volume ratio of 1,4-dichlorobenzyl, intermediate (I), potassium hydroxide, and dichloromethane was 0.2 g:2.2–2.3 g:0.4–0.5 g:25 mL; during purification, recrystallization was performed, and the volume ratio of petroleum ether to dichloromethane in the solvent was 20:1.

[0017] In step 3, the reaction is carried out at 25–30°C; the reaction time is 4–5 h; the molar ratio of intermediate (II) to paraformaldehyde is 1.0:3.0–3.3; the molar ratio of intermediate (II) to boron trifluoride ethyl ether is 1.0:1.2–1.3; the mass-to-volume ratio of intermediate (II), paraformaldehyde, boron trifluoride ethyl ether, and dichloromethane is 0.33 g:0.03–0.04 g:0.06–0.07 g:20 mL; column chromatography is used for purification, and the volume ratio of petroleum ether to dichloromethane in the eluent is 10:1.

[0018] A capillary gas chromatography column is prepared by a static method using alkyl-functionalized hexafluorocarbons as the stationary phase.

[0019] An application of a capillary gas chromatography column, which can separate substituted benzaldehyde isomers, aniline isomers, halobenzene isomers, 8 groups of cis-trans isomers, and 21 complex mixtures; among which...

[0020] Substituted benzaldehyde isomers include: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, o-cyanobenzaldehyde, m-cyanobenzaldehyde, p-cyanobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde.

[0021] Aniline isomers include: o-iodoaniline, m-iodoaniline, and p-iodoaniline;

[0022] Halogenated benzene isomers include: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene;

[0023] The eight cis-trans isomers include: cis-3,3,5-trimethylcyclohexane salicylate and trans-3,3,5-trimethylcyclohexane salicylate, cis-1,3-dimethylcyclohexane and trans-1,3-dimethylcyclohexane, cis-nerolidol and trans-nerolidol, cis-nerolidol and trans-nerolidol, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-decahydronaphthalene and trans-decahydronaphthalene, cis-2,5-dimethoxytetrahydrofuran and trans-2,5-dimethoxytetrahydrofuran, and cis-2,5-dihydro-2,5-dimethoxytetrahydrofuran and trans-2,5-dihydro-2,5-dimethoxytetrahydrofuran.

[0024] The complex mixture of 21 components includes: 2-hexanone, 1-bromopentane, o-xylene, o-chlorotoluene, 2-octanone, 1,2,3-trimethylbenzene, m-dichlorobenzene, 1-octanol, methyl octanoate, o-toluidine, n-dodecane, 1,3,5-trichlorobenzene, 2,6-dimethylbenzene, 2,3-xylenol, n-tetane, m-chloroaniline, m-chloronitrobenzene, 2-methylnaphthalene, methyl undecanoate, m-bromonitrobenzene, and n-pentadecane.

[0025] Advantages and effects of the technical solution of this invention:

[0026] (1) This invention uses 1,4-benzenediol as a raw material. First, intermediate (I) is obtained through an etherification reaction. Then, intermediate (I) undergoes a Friedel-Crafts alkylation reaction to obtain intermediate (II). Intermediate (II) undergoes a cyclization reaction to obtain an alkyl-functionalized hexaaromatic hydrocarbon (III) for use as a stationary phase, named DeLP6A, as shown below. Figure 1 As shown. The reaction conditions were mild and the cost was low throughout the experiment. The alkyl-functionalized hexaaromatic hydrocarbon used as the stationary phase has a novel structure and provides significant separation of analytes. The final product exhibits good stability.

[0027] (2) The alkyl-functionalized hexacyclic aromatic hydrocarbon DeLP6A for stationary phase prepared in this invention combines the structural characteristics of hexacyclic aromatic hydrocarbons with the advantages of alkyl functionalization. Among them, hexacyclic aromatic hydrocarbons have excellent host-guest properties, structural flexibility and cavity adaptability, and are easy to functionalize. This allows for the introduction of long alkyl chains along the lower edge of the hexacyclic aromatic hydrocarbon, thereby improving the properties of hexacyclic aromatic hydrocarbons as gas chromatography stationary phases. The introduction of long alkyl chains can lower the melting point of hexacyclic aromatic hydrocarbons, improve the film-forming properties, thermal stability, and separation performance of hexacyclic aromatic hydrocarbons as chromatographic stationary phases for target compounds.

[0028] (3) The alkyl-functionalized hexaaromatic hydrocarbon DeLP6A prepared by the present invention has a unique cyclic structure and alkoxy chain functional groups, which makes this stationary phase have good performance in practical applications. It has a variety of weak interaction forces with different analytes, including van der Waals forces, hydrogen bonds, π-π interactions, dipole-dipole interactions, etc., which makes the DeLP6A column have good separation performance.

[0029] (4) This invention is the first to use DeLP6A as the stationary phase of a capillary gas chromatography column. DeLP6A perfectly combines the structural characteristics of clinoary hydrocarbons with the advantages of alkyl functionalization, making it possible for this type of novel material to be used as the stationary phase of a capillary gas chromatography column, and providing richer separation materials for chromatographic separation research.

[0030] (5) This invention is the first to use DeLP6A as the stationary phase in a capillary gas chromatography column, which exhibits good thermal stability up to 308℃. Figure 2 As shown.

[0031] (6) This invention is the first to use DeLP6A as the chromatographic stationary phase. A capillary gas chromatographic column prepared by the static coating method exhibits high column efficiency, such as... Figure 3 As shown.

[0032] (7) The capillary gas chromatographic column prepared by this invention has good separation performance for different analytes and can separate substituted benzaldehyde isomers, including methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde; bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde; cyanobenzaldehyde isomers: o-cyanobenzaldehyde, m-cyanobenzaldehyde, and p-cyanobenzaldehyde; and nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde. The separation effect is superior to that of commercial polysiloxane columns HP-5 and HP-35. Figure 4 As shown.

[0033] Substituted aniline isomers, including iodoaniline isomers: o-iodoaniline, m-iodoaniline, and p-iodoaniline, offer superior separation performance compared to commercial polysiloxane columns HP-5 and HP-35, such as... Figure 5 As shown.

[0034] Substituted halobenzene isomers, including chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene; dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, p-dibromobenzene; dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene; and chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, exhibit superior separation performance compared to commercial polysiloxane columns HP-5 and HP-35. Figure 6 As shown.

[0035] Eight groups of cis-trans isomers, including cis-3,3,5-trimethylcyclohexane salicylate and trans-3,3,5-trimethylcyclohexane salicylate, cis-1,3-dimethylcyclohexane and trans-1,3-dimethylcyclohexane, cis-nerolidol and trans-nerolidol, cis-nerolidol and trans-nerolidol, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-decahydronaphthalene and trans-decahydronaphthalene, cis-2,5-dimethoxytetrahydrofuran and trans-2,5-dimethoxytetrahydrofuran, cis-2,5-dihydro-2,5-dimethoxytetrahydrofuran and trans-2,5-dihydro-2,5-dimethoxytetrahydrofuran, such as... Figure 7 As shown.

[0036] This column can handle a complex mixture of 21 components, including: 2-hexanone, 1-bromopentane, o-xylene, o-chlorotoluene, 2-octanone, 1,2,3-trimethylbenzene, m-dichlorobenzene, 1-octanol, methyl octanoate, o-toluidine, n-dodecane, 1,3,5-trichlorobenzene, 2,6-dimethylbenzene, 2,3-xylenol, n-tetane, m-chloroaniline, m-chloronitrobenzene, 2-methylnaphthalene, methyl undecanoate, m-bromonitrobenzene, and n-pentadecane. The separation performance is superior to that of commercial polysiloxane columns HP-5 and HP-35. Figure 8 As shown.

[0037] (8) The capillary gas chromatography column prepared in this invention exhibits excellent separation performance for benzaldehyde isomers and halogenated benzene isomers, including chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene; chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene; and methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde. Its separation effect is superior to that of commercial polysiloxane columns HP-5 and HP-35, and capillary gas chromatography columns prepared from alkyl-functionalized hexaaromatic hydrocarbons, such as... Figure 9 As shown. Attached Figure Description

[0038] The above and other objects, features, and advantages of exemplary embodiments of the present invention will become readily apparent upon reading the following detailed description with reference to the accompanying drawings. In the drawings, several embodiments of the invention are illustrated by way of example and not limitation, with the same or corresponding reference numerals denoteing the same or corresponding parts, wherein:

[0039] Figure 1 This is a reaction diagram of the alkyl-functionalized hexafluorocarbon DeLP6A prepared from 1,4-benzenediol as a raw material according to the present invention.

[0040] Figure 2 This is a thermogravimetric diagram of an alkyl-functionalized clinoaryl stationary phase.

[0041] Figure 3 The column efficiency (Golay curve) of the capillary gas chromatographic column prepared in this invention was obtained by measuring n-dodecane as the analyte at 120°C.

[0042] Figure 4 This invention provides a capillary gas chromatography column for separating benzaldehyde isomers of different polarities and types, and compares it with commercial columns HP-5 and HP-35. The isomers include methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde; bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde; cyanobenzaldehyde isomers: o-cyanobenzaldehyde, m-cyanobenzaldehyde, and p-cyanobenzaldehyde; and nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde.

[0043] Figure 5 The capillary gas chromatography column prepared in this invention is used to separate iodoaniline isomers, and the commercial columns HP-5 and HP-35 are used as a reference for separating o-iodoaniline, m-iodoaniline, and p-iodoaniline.

[0044] Figure 6 This invention provides a capillary gas chromatography column for separating different types and polarities of halogenated benzene isomers, as well as a comparison with commercial columns HP-5 and HP-35. The isomers include chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene; dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, and p-dibromobenzene; dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; and chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene.

[0045] Figure 7 This invention provides a capillary gas chromatography column for separating eight groups of cis-trans isomers of different polarities, including (a) cis-3,3,5-trimethylcyclohexane salicylate and trans-3,3,5-trimethylcyclohexane salicylate, (b) cis-1,3-dimethylcyclohexane and trans-1,3-dimethylcyclohexane, (c) cis-nerolidol and trans-nerolidol, and (d) cis-nerolidol. Chromatograms of trans-nerolidol, (e): cis-4-tert-butylcyclohexanol, trans-4-tert-butylcyclohexanol, (f): cis-decahydronaphthalene, trans-decahydronaphthalene, (g): cis-2,5-dimethoxytetrahydrofuran, trans-2,5-dimethoxytetrahydrofuran, (h): cis-2,5-dihydro-2,5-dimethoxyfuran, trans-2,5-dihydro-2,5-dimethoxyfuran.

[0046] Figure 8 This invention provides a capillary gas chromatography column for separating 21 complex mixture samples of different polarities and types, and compares it with commercial columns HP-5 and HP-35.

[0047] Figure 9 This invention provides a capillary gas chromatography column for separating benzaldehyde and halogenated benzene isomers, compared with commercial HP-5, HP-35, and P6A-C10 columns. The column includes chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene; chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene; and methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde.

[0048] Explanation of icon numbers:

[0049] 1: 2-Hexanone, 2: 1-Bromopentane, 3: o-xylene, 4: o-chlorotoluene, 5: 2-octanone, 6: 1,2,3-trimethylbenzene, 7: m-dichlorobenzene, 8: 1-octanol, 9: methyl octanoate, 10: o-toluidine, 11: n-dodecane, 12: 1,3,5-trichlorobenzene, 13: 2,6-dimethylbenzene, 14: 2,3-dimethylphenol, 15: n-tetane, 16: m-chloroaniline, 17: m-chloronitrobenzene, 18: 2-methylnaphthalene, 19: methyl undecanoate, 20: m-bromonitrobenzene, 21: n-pentadecane. Detailed Implementation

[0050] Exemplary embodiments of the present disclosure will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Unless otherwise specified, the techniques used in the embodiments are conventional means well known to those skilled in the art.

[0051] The principle of this invention:

[0052] like Figure 1 As shown, this invention uses 1,4-benzenediol as a raw material. First, intermediate (I) is obtained through etherification reaction. Then, intermediate (I) is subjected to Friedel-Crafts alkylation reaction to obtain intermediate (II). Intermediate (II) is subjected to cyclization reaction to obtain alkyl-functionalized hexane DeLP6A (III). The obtained DeLP6A has a uniform particle size distribution on the chromatographic column.

[0053] The alkyl-functionalized hexacyclic aromatic hydrocarbon DeLP6A prepared in this invention combines the structural characteristics of hexacyclic aromatic hydrocarbons with the advantages of alkyl functionalization. Hexacyclic aromatic hydrocarbons possess advantages such as good structural flexibility, excellent host-guest properties, and good cavity adaptability. Furthermore, hexacyclic aromatic hydrocarbons are easily derivatized; introducing nonpolar long alkyl chains improves the properties of hexacyclic aromatic hydrocarbons as gas chromatography stationary phases, lowering their melting point, improving their film-forming properties, thermal stability, and separation performance of target compounds when used as chromatographic stationary phases.

[0054] This invention first uses the traditional sodium chloride microcrystal deposition method to roughen the inner surface of the capillary column for column pretreatment. Then, a static coating method is used to prepare the column, so that the stationary phase is evenly dispersed on the inner wall of the capillary column. Finally, the coated capillary column is aged under nitrogen protection using a programmed temperature increase method, thus completing the preparation of the DeLP6A capillary column.

[0055] The method for synthesizing the alkyl-functionalized hexane DeLP6A for the stationary phase of the present invention uses 1,4-benzenediol as a raw material. First, an intermediate (Ⅰ) is obtained through an etherification reaction. Then, intermediate (Ⅰ) is subjected to a Friedel-Crafts alkylation reaction to obtain intermediate (Ⅱ). Intermediate (Ⅱ) is subjected to a cyclization reaction to obtain the alkyl-functionalized hexane derivative DeLP6A (Ⅲ).

[0056] Example 1:

[0057]

[0058] 1.00 g (9.08 mmol) of 1,4-benzenediol, 6.03 g (27.24 mmol) of 1-bromodecane, 1.53 g (27.24 mmol) of potassium hydroxide, and 22 mL of ethanol were reacted at 80 °C for 5.5 h. Deionized water was added to precipitate a solid. After standing and cooling, the solid was filtered. The filter cake was dried to obtain the crude product, which was recrystallized at 70 °C using ethanol as a solvent until the solution became clear. The solution was then allowed to stand, and a solid precipitated. This solid was filtered, and the filter cake was dried to obtain intermediate (Ⅰ) – a white solid: 2.60 g. mp 70.1-70.8 °C. IR (KBr, cm⁻¹) -1 ): 1028.65(COC), 1231.65(COC), 1409.22(C=C), 1463.21(C=C), 1473.74(C=C), 1509.98(C=C), 2849.81(CH2), 2871.68(CH2), 2955.00(CH3).

[0059]

[0060] 2.23 g (5.17 mmol) of intermediate (I) obtained in step (1), 0.20 g (1.14 mmol) of 1,4-dichlorobenzyl chloride, 0.46 g (3.43 mmol) of aluminum trichloride and 25 mL of dichloromethane were added to a 50 mL single-necked flask and reacted at 25 °C for 2.5 h. Deionized water was added, the mixture was separated, the organic layer was dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness to obtain 2.21 g of pale yellow crude product. The product was purified by column chromatography with petroleum ether:dichloromethane = 20:1 (V:V) as the eluent to obtain intermediate (II) white solid: 0.38 g. 1H NMR(400MHz, CDCl3)δ:7.00(s,4H),6.88(s,6H),4.15-3.44(m,12H),1.85-1.72(m,8H),1.65( q,J=6.8Hz,4H),1.5-1.43(m,4H),1.40-1.27(m,48H),0.91(td,J=6.8,3.2Hz,12H).IR(KBr,cm -1 ): 1038.67(COC), 1239.75(COC), 1412.28(C=C), 1471.25(C=C), 1483.91(C=C), 2854.82(CH2), 2868.17(CH2), 2953.99(CH3).

[0061]

[0062] 0.32 g (0.37 mmol) of intermediate (II), 0.3 g (1.10 mmol) of paraformaldehyde and 20 mL of dichloromethane obtained in step (2) were added to a 50 mL single-necked flask and reacted at 0 °C for 20 min. Then, 0.06 g (0.44 mmol) of boron trifluoride ether was added and the reaction was carried out at 30 °C for 4 h. The reaction was quenched by adding sodium hydroxide aqueous solution. The organic phase was washed with saturated sodium chloride solution, filtered, and evaporated to dryness to obtain 0.35 g of crude product. The crude product was purified by column chromatography with petroleum ether:dichloromethane = 10:1 (V:V) as the eluent to obtain a colorless oily substance DeLP6A(Ⅲ): 0.11 g. 1 H NMR(300MHz, CDCl3)δ:6.97(s,8H),6.85(s,4H),6.56(s,4H),4.10-3.52(m,28H),1.76(m,8H),1.59(g ,J=6.7Hz,8H),1.43(d,J=7.9Hz,8H),1.27(d,J=7.4Hz,104H),0.88(td,J=6.8,2.6Hz,24H).IR(KBr,cm -1 ):1046.77(COC),1393.48(COC),1409.22(C=C),1467.59(C=C),1504.16(C=C),2850.86(CH2),2920.03(CH2).ESI-MS:m / z calculated for C 122 H 196 O8:1789.90(100%); found:1808.53[M+H2O+H] + (100%) 1846.56 [M+H2O+K] +(100%).

[0063] Example 2:

[0064] The difference between this experiment and Example 1 is that the reaction conditions are different.

[0065] 1.50 g (13.62 mmol) of 1,4-benzenediol, 9.25 g (41.86 mmol) of 1-bromodecane, 2.35 g (41.94 mmol) of potassium hydroxide and 35 mL of ethanol were reacted at 83 °C for 5.1 h. Deionized water was added to precipitate the solid. After standing and cooling, the solid was filtered. The filter cake was dried to obtain the crude product. The crude product was recrystallized at 70 °C using ethanol as a solvent until the solution was clear. After standing, the solid precipitated. The solid was filtered and the filter cake was dried to obtain intermediate (Ⅰ) white solid: 3.92 g.

[0066] 3.92 g (10.24 mmol) of intermediate (Ⅰ) obtained in step (1), 0.3 g (1.71 mmol) of 1,4-dichlorobenzyl, 0.70 g (5.21 mmol) of aluminum trichloride and 38 mL of dichloromethane were added to a 100 mL single-necked flask and reacted at 25 °C for 2.8 h. Deionized water was added, the mixture was separated, the organic layer was dried with anhydrous magnesium sulfate, filtered, and evaporated to dryness to obtain 3.48 g of pale yellow crude product. The product was purified by column chromatography with petroleum ether:dichloromethane = 20:1 (V:V) as the eluent to obtain intermediate (Ⅱ) white solid: 0.55 g.

[0067] 0.49 g (0.55 mmol) of intermediate (II), 0.05 g (1.20 mmol) of paraformaldehyde and 30 mL of dichloromethane obtained in step (2) were added to a 50 mL single-necked flask and reacted at 0 °C for 20 min. Then, 0.10 g (0.70 mmol) of boron trifluoride ether was added and the reaction was carried out at 28 °C for 4.6 h. The reaction was quenched by adding sodium hydroxide aqueous solution. The organic phase was washed with saturated sodium chloride solution, filtered, and evaporated to dryness to obtain 0.54 g of crude product. The crude product was purified by column chromatography with petroleum ether:dichloromethane = 10:1 (V:V) as the eluent to obtain a colorless oily substance DeLP6A(Ⅲ): 0.11 g.

[0068] Example 3:

[0069] The difference between this experiment and Example 1 is that the reaction conditions are different.

[0070] 1.75 g (15.89 mmol) of 1,4-benzenediol, 10.89 g (49.29 mmol) of 1-bromodecane, 2.77 g (49.44 mmol) of potassium hydroxide and 44 mL of ethanol were reacted at 85 °C for 4.5 h. Deionized water was added to precipitate the solid. After standing and cooling, the solid was filtered. The filter cake was dried to obtain the crude product. The crude product was recrystallized at 70 °C using ethanol as a solvent until the solution was clear. After standing, the solid precipitated. The solid was filtered and the filter cake was dried to obtain intermediate (Ⅰ) white solid: 4.71 g.

[0071] The 4.64 g (12.12 mmol) of intermediate (Ⅰ) obtained in step (1), the compound (I) obtained, 0.35 g (2.00 mmol) of 1,4-dichlorobenzyl, 0.83 g (6.18 mmol) of aluminum trichloride and 44 mL of dichloromethane were added to a 100 mL single-necked flask and reacted at 25 °C for 3 h. Deionized water was added, the mixture was separated, the organic layer was dried with anhydrous magnesium sulfate, filtered, and evaporated to dryness to obtain 3.98 g of pale yellow crude product. The product was purified by column chromatography with petroleum ether:dichloromethane = 20:1 (V:V) as the eluent to obtain intermediate (Ⅱ) white solid: 0.71 g.

[0072] 0.57 g (0.65 mmol) of intermediate (II), 0.06 g (2.12 mmol) of paraformaldehyde and 35 mL of dichloromethane obtained in step (2) were added to a 100 mL single-necked flask and reacted at 0 °C for 20 min. Then, 0.12 g (0.83 mmol) of boron trifluoride ether was added and the reaction was carried out at 25 °C for 5 h. The reaction was quenched by adding sodium hydroxide aqueous solution. The organic phase was washed with saturated sodium chloride solution, filtered, and evaporated to dryness to obtain 0.71 g of crude product. The crude product was purified by column chromatography with petroleum ether:dichloromethane = 10:1 (V:V) as the eluent to obtain a colorless oily substance DeLP6A(Ⅲ): 0.21 g.

[0073] Example 4:

[0074] Preparation of the capillary gas chromatography column of this invention:

[0075] (1) Cut a quartz capillary with a length of 5m and an inner diameter of 250μm. First, rinse it with dichloromethane for 10min, and then age it at 200℃ for 2-3h under nitrogen protection so that the impurities in the capillary column are released with the nitrogen flow at high temperature.

[0076] (2) Weigh 1.31 g of ground NaCl powder and place it in 10 mL of anhydrous methanol solution. Stir vigorously for 45 min to obtain a saturated sodium chloride methanol solution. Add 6 mL of the saturated solution to 8 mL of vigorously stirred dichloromethane solution, then add 0.6 mL of anhydrous methanol solution and stir for 5 min. Add another 8 mL of dichloromethane solution and continue stirring for 2 min to obtain a saturated colloidal solution. This completes the roughening of the inner surface of the capillary column.

[0077] (3) Under appropriate nitrogen pressure, the saturated colloidal solution was pressed into the capillary tube, and then the solution in the column was blown out with nitrogen. Under nitrogen protection, it was recrystallized at 200°C for 3 hours.

[0078] (4) In this experiment, the static column preparation method was used. DeLP6A was dissolved in dichloromethane solution to prepare a stationary solution with a concentration of 0.15% (w / v). The stationary solution was sonicated for 5 min to remove air bubbles.

[0079] (5) Use a syringe to push the stationary phase into the capillary column until the stationary phase fills the entire column. Then seal one end of the capillary and connect the other end to the vacuum system. In a constant temperature water bath at 38°C, the solvent will slowly evaporate and the stationary phase will be evenly dispersed on the inner wall of the capillary column.

[0080] (6) The coated capillary column was aged under nitrogen protection using a programmed temperature increase method: it was kept at 40℃ for 30 min, and then increased to 180℃ at a rate of 1℃ / min and kept for 7 h to complete the aging of the column and obtain the capillary gas chromatography column.

[0081] Example 5:

[0082] Example of separation performance using a capillary gas chromatography column:

[0083] (1) As Figure 3 As shown, the Golay curve of n-dodecane was determined using the capillary gas chromatography column prepared in Example 4. The specific chromatographic conditions were: column oven temperature 120°C, carrier gas: nitrogen, carrier gas flow rate: 17.14 cm / s, and minimum theoretical plate height: 0.21 mm.

[0084] (2) Separation of substituted benzaldehyde isomers using a capillary gas chromatography column prepared in the examples

[0085] Different types and polarities of benzaldehyde isomers were selected as analytes for separation, including methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde; bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde; cyanobenzaldehyde isomers: o-cyanobenzaldehyde, m-cyanobenzaldehyde, and p-cyanobenzaldehyde; and nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde. Chromatographic separation conditions: 40℃ for 1 min, then increased to 160℃ at a rate of 10℃ / min; carrier gas flow rate: 0.6 mL / min.

[0086] Figure 4 This is a chromatogram comparing the separation of benzaldehyde isomers of different polarities and types using a capillary gas chromatography column with that of commercial columns HP-5 and HP-35. The results are superior to those of commercial polysiloxane columns HP-5 and HP-35.

[0087] (3) Separation of iodoaniline isomers using a capillary gas chromatography column prepared in the example

[0088] Figure 5 This is a chromatogram comparing the separation of iodoaniline isomers (o-iodoaniline, m-iodoaniline, and p-iodoaniline) using the capillary gas chromatography column prepared in this example with that of commercial columns HP-5 and HP-35. The capillary gas chromatography column prepared in this example can effectively separate substituted aniline isomers, and its performance is superior to that of the commercial polysiloxane columns HP-5 and HP-35. Chromatographic separation conditions: 40°C for 1 min, then increased to 160°C at a rate of 10°C / min, with a carrier gas flow rate of 0.6 mL / min.

[0089] (4) The capillary gas chromatography column prepared in the example was used to separate substituted halobenzene isomers.

[0090] Different types and polarities of halogenated benzene isomers were selected as analytes for separation, including chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene; dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, and p-dibromobenzene; dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; and chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene. Chromatographic separation conditions: 40℃ for 1 min, then increased to 160℃ at a rate of 10℃ / min, with a carrier gas flow rate of 0.6 mL / min.

[0091] Figure 6 This is a chromatogram comparing the separation of halobenzene isomers using a capillary gas chromatography column prepared in the example with that using commercial columns HP-5 and HP-35, as shown below. Figure 6 As shown, the capillary gas chromatography column prepared in the examples can effectively separate halobenzene isomers, and its performance is better than that of commercial polysiloxane columns HP-5 and HP-35.

[0092] (6) The capillary gas chromatography column prepared in the example separated 8 groups of cis-trans isomers.

[0093] Eight cis-trans isomers were selected as analytes, and the isomers were separated using a capillary gas chromatography column prepared in the example. Chromatographic separation conditions: 40℃ for 1 min, then increased to 160℃ at a rate of 10℃ / min, with a carrier gas flow rate of 0.6 mL / min.

[0094] Figure 7 This is a chromatogram of nine cis-trans isomers of different polarities separated by a capillary gas chromatography column prepared in the example, wherein (a): cis-3,3,5-trimethylcyclohexane salicylate and trans-3,3,5-trimethylcyclohexane salicylate, (b): cis-1,3-dimethylcyclohexane and trans-1,3-dimethylcyclohexane, (c): cis-nerolidol and trans-nerolidol, (d): cis- (e) cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, (f) cis-decahydronaphthalene and trans-decahydronaphthalene, (g) cis-2,5-dimethoxytetrahydrofuran and trans-2,5-dimethoxytetrahydrofuran, (h) cis-2,5-dihydro-2,5-dimethoxyfuran and trans-2,5-dihydro-2,5-dimethoxyfuran. Figure 7 As shown, the capillary gas chromatography column prepared in the example can completely separate each group of cis-trans isomers, demonstrating the advantages of the DeLP6A stationary phase in separating cis-trans isomers, and the separation is fast and efficient.

[0095] (7) Capillary gas chromatography column prepared in the example for separating 21 complex mixtures

[0096] Twenty-one complex mixtures were selected as analytes, and the samples were separated using the capillary gas chromatography column prepared in the example. Chromatographic separation conditions: 40℃ for 1 min, then increased to 160℃ at a rate of 10℃ / min, with a carrier gas flow rate of 0.6 mL / min.

[0097] Figure 8 This is a chromatogram of a complex mixture of 21 components separated by capillary gas chromatography, where: 1: 2-hexanone, 2: 1-bromopentane, 3: o-xylene, 4: o-chlorotoluene, 5: 2-octanone, 6: 1,2,3-trimethylbenzene, 7: m-dichlorobenzene, 8: 1-octanol, 9: methyl octanoate, 10: o-toluidine, 11: n-dodecane, 12: 1,3,5-trichlorobenzene, 13: 2,6-dimethylbenzene, 14: 2,3-xylenol, 15: n-tetane, 16: m-chloroaniline, 17: m-chloronitrobenzene, 18: 2-methylnaphthalene, 19: methyl undecanoate, 20: m-bromonitrobenzene, 21: n-pentadecane. Figure 8As shown, the capillary gas chromatography column prepared through the examples exhibits good separation performance for a complex mixture of 21 components, with a wide variety of analytes and a broad polarity range. This demonstrates the excellent suitability of the DeLP6A stationary phase for separating complex mixtures, and its separation performance is superior to that of commercial polysiloxane columns HP-5 and HP-35.

[0098] Figure 9 The capillary gas chromatography column prepared in this example separates benzaldehyde isomers and halobenzene isomers. Benzaldehyde isomers and halobenzene isomers were selected as the analytes for separation, including chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene; chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene; and methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde. Chromatographic separation conditions: 40℃ for 1 min, then increased to 160℃ at a rate of 10℃ / min; carrier gas flow rate: 0.6 mL / min.

[0099] Figure 9 The chromatograms shown are comparisons between the separation of benzaldehyde isomers and halogenated benzene isomers using the capillary gas chromatography column prepared in the examples and the separation by commercial columns HP-5, HP-35, and P6A-C10. Figure 9 As shown, the capillary gas chromatography column prepared in the examples can effectively separate benzaldehyde and halobenzene isomers, and its performance is better than that of commercial polysiloxane columns HP-5 and HP-35 and capillary gas chromatography columns prepared with alkyl-functionalized hexaaromatics.

[0100] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

[0101] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An alkyl-functionalized hexafluorocarbon for use as a stationary phase, characterized in that, The chemical structural formula of alkyl-functionalized hexane is: 。 2. A method for preparing alkyl-functionalized hexafluorocarbons for a stationary phase as described in claim 1, characterized in that, The specific steps of this preparation method include: Step 1, Monohalogenated Hydrocarbon Etherification: 1,4-benzenediol was reacted with 1-bromodecane, potassium hydroxide, and ethanol by heating. After the reaction was complete, the mixture was cooled, post-processed, and purified to obtain intermediate (Ⅰ). The structural formula of intermediate (Ⅰ) is as follows: ； Step 2, Friedel-Crafts alkylation: The intermediate (Ⅰ) obtained in Step 1, 1,4-dichlorobenzyl chloride, aluminum trichloride, and dichloromethane are reacted at room temperature. After the reaction is complete, post-processing and purification are performed to obtain intermediate (Ⅱ); the structural formula of intermediate (Ⅱ) is as follows: ； Step 3, Cyclolysis: The intermediate (II) obtained in step 2, paraformaldehyde, boron trifluoride ether and dichloromethane are mixed. After the reaction is completed, DeLP6A (III) is obtained after post-processing and purification. The structural formula of DeLP6A(Ⅲ): ； The prepared DeLP6A(Ⅲ) had a uniform particle size distribution on a capillary gas chromatography column.

3. The method for preparing alkyl-functionalized hexafluorocarbons for the stationary phase according to claim 1, characterized in that: The heating reaction in step 1 is carried out at a temperature of 80-85°C; the reaction time is 4.5-5.5 h; the temperature is then lowered to 25°C; the molar ratio of 1,4-benzenediol to 1-bromodecane is 1.0:3.0-3.1; the molar ratio of 1,4-benzenediol to potassium hydroxide is 1.0:3.0-3.1; and the product is purified by recrystallization using ethanol as the solvent.

4. The method for preparing alkyl-functionalized hexafluorocarbons for the stationary phase according to claim 2, characterized in that: The reaction in step 2 is carried out at 25°C; the reaction time range is 2-3 h; the molar ratio of 1,4-dichlorobenzyl to intermediate (Ⅰ) is 1.0:5.0-5.1; the molar ratio of 1,4-dichlorobenzyl to potassium hydroxide is 1.0:3.0-3.1; during purification, recrystallization is performed, and the volume ratio of petroleum ether to dichloromethane in the solvent is 20:

1.

5. The method for preparing alkyl-functionalized hexafluorocarbons for the stationary phase according to claim 2, characterized in that: The reaction in step 3 is carried out at 25~30℃; the reaction time range is 4~5 h; the molar ratio of intermediate (II) to paraformaldehyde is 1.0:3.0~3.3; the molar ratio of intermediate (II) to boron trifluoride ether is 1.0:1.2~1.3; column chromatography is used for purification, and petroleum ether is used as the eluent; the volume ratio of dichloromethane is 10:

1.

6. A capillary gas chromatography column, characterized in that: The alkyl-functionalized hexaaromatic hydrocarbons obtained by the preparation method described in claim 2 were used to prepare a capillary gas chromatography column by a static method.

7. An application of the capillary gas chromatography column as described in claim 6, characterized in that: Capillary gas chromatography columns can separate substituted benzaldehyde isomers, aniline isomers, halobenzene isomers, 8 groups of cis-trans isomers, and 21 complex mixtures; among them, Substituted benzaldehyde isomers include: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, o-cyanobenzaldehyde, m-cyanobenzaldehyde, p-cyanobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde. Aniline isomers include: o-iodoaniline, m-iodoaniline, and p-iodoaniline; Halogenated benzene isomers include: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene; The eight cis-trans isomers include: cis-3,3,5-trimethylcyclohexane salicylate and trans-3,3,5-trimethylcyclohexane salicylate, cis-1,3-dimethylcyclohexane and trans-1,3-dimethylcyclohexane, cis-nerolidol and trans-nerolidol, cis-nerolidol and trans-nerolidol, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-decahydronaphthalene and trans-decahydronaphthalene, cis-2,5-dimethoxytetrahydrofuran and trans-2,5-dimethoxytetrahydrofuran, and cis-2,5-dihydro-2,5-dimethoxytetrahydrofuran and trans-2,5-dihydro-2,5-dimethoxytetrahydrofuran. The complex mixture of 21 components includes: 2-hexanone, 1-bromopentane, o-xylene, o-chlorotoluene, 2-octanone, 1,2,3-trimethylbenzene, m-dichlorobenzene, 1-octanol, methyl octanoate, o-toluidine, n-dodecane, 1,3,5-trichlorobenzene, 2,6-dimethylbenzene, 2,3-xylenol, n-tetane, m-chloroaniline, m-chloronitrobenzene, 2-methylnaphthalene, methyl undecanoate, m-bromonitrobenzene, and n-pentadecane.

Images