An alkyl-functionalized cyclotriveratrylene, its preparation method, capillary gas chromatography column and application

Abstract

An alkyl-functionalized cyclotriveratrylene, its preparation method, capillary gas chromatography column and application relate to the technical field of gas chromatography analysis. In this preparation method, 1,2-dihydroxybenzene is used as a raw material. First, intermediate I is obtained through an etherification reaction. Secondly, the alkyl-functionalized cyclotriveratrylene is obtained by subjecting intermediate I to a cyclization reaction. By introducing a long alkyl chain at the lower edge of the cyclotriveratrylene, the properties of the cyclotriveratrylene as a stationary phase of the capillary gas chromatography column are improved. Introducing the long alkyl chain can reduce the melting point of the cyclotriveratrylene, improve the film-forming property, thermal stability of the cyclotriveratrylene, and the separation performance of the cyclotriveratrylene used as a chromatographic stationary phase for analytes.

Description

Technical Field

[0001] The present invention relates to the technical field of gas chromatography analysis, and specifically relates to an alkyl-functionalized cyclotriveratrylene, a preparation method thereof, a capillary gas chromatography column, and an application thereof. Background Art

[0002] Gas chromatography has the characteristics of high efficiency, high sensitivity, strong selectivity, fast analysis speed, wide application, and simple operation. It is suitable for the qualitative and quantitative analysis of volatile organic compounds. For non-volatile liquids and solid substances, they can be analyzed after high-temperature pyrolysis and gasification. Gas chromatography can be used in combination with infrared absorption spectrometry or mass spectrometry. Using chromatography as a means of separating complex samples can achieve high accuracy.

[0003] The chromatographic column is the core of gas chromatography and an important device for separation and detection. The stationary phase material on the chromatographic column is the key. Existing commercial chromatographic column materials such as polysiloxanes and polyethylene glycols can already achieve good separation of most substances. When facing the separation of some mixtures with extremely close boiling points and polarities, or positional isomers and cis-trans isomers, the available materials are very limited. Therefore, new capillary gas chromatography stationary phases with special selectivity and high stability are still being continuously explored.

[0004] Macrocyclic compounds such as cyclotriveratrylene, columnar hexaphenylene, and columnar pentaphenylene have become the main research objects of scientific research personnel due to their inherent molecular recognition and complexation functions.

[0005] Reference 1: The thesis "Research on the Separation Performance and Application of Novel Gas Chromatography Stationary Phases of Cyclotriveratrylene and Triindene, Lu Qing, Beijing Institute of Technology, June 2016".

[0006] Reference 1 discloses that the CTV (cyclotriveratrylene) column has good separation effects on alkanes, esters, haloalkanes, halobenzenes, plasticizers, various positional isomers, and cis-trans isomers. However, the film-forming property and thermal stability of cyclotriveratrylene are relatively general. When it is used as the stationary phase of a capillary gas chromatography column, it still cannot effectively separate chloronitrobenzene isomers, benzenediol isomers, and phenylenediamine isomers.

[0007] Reference 2: Chinese patent document with the publication number CN 115636737 A.

[0008] Reference 2 discloses an alkyl-functionalized columnar hexaphenylene stationary phase, a capillary gas chromatography column, a preparation method thereof, and an application thereof. However, the separation effect of this alkyl-functionalized columnar hexaphenylene stationary phase on chloronitrobenzene isomers, benzenediol isomers, and phenylenediamine isomers is still poor. Summary of the Invention

[0009] The present invention aims to provide an alkyl-functionalized cyclotriveratrylene, its preparation method, a capillary gas chromatography column and applications, so as to solve the problem in the prior art that macrocyclic compounds have poor separation effects on p-chloronitrobenzene isomers, benzenediol isomers and phenylenediamine isomers.

[0010] To achieve the above object, the specific solution adopted by the present invention is: An alkyl-functionalized cyclotriveratrylene, the chemical structural formula of the alkyl-functionalized cyclotriveratrylene is .

[0011] A preparation method of an alkyl-functionalized cyclotriveratrylene, comprising the following steps:

[0012] S1. Take 1,2-dihydroxybenzene, 1-bromodecane, potassium carbonate and N,N-dimethylformamide for an etherification reaction to obtain intermediate I, and the chemical structural formula of intermediate I is ;

[0013] S2. Take intermediate I, paraformaldehyde, sulfuric acid and glacial acetic acid for a cyclization reaction. After the reaction is completed, through post-treatment and purification, the alkyl-functionalized cyclotriveratrylene is prepared.

[0014] As a further optimization of the above technical solution, the temperature of the etherification reaction is 60-65°C, the reaction time is 23-24 h, after the reaction is completed, the temperature is lowered to 25°C, and dichloromethane is used as the eluent for column chromatography purification of the reaction product to obtain intermediate I.

[0015] As a further optimization of the above technical solution, in step S1, the molar ratio of 1,2-dihydroxybenzene, 1-bromodecane and potassium carbonate is 1.0: 2.9-3.0: 3.9-4.0.

[0016] As a further optimization of the above technical solution, the reaction temperature of the cyclization reaction is 25-30°C, the reaction time is 5-6 h, the reaction product is subjected to column chromatography purification, and the volume ratio of petroleum ether to dichloromethane in the eluent is 5:1.

[0017] As a further optimization of the above technical solution, in step S2, the molar ratio of intermediate I, paraformaldehyde and sulfuric acid is 1.0: 0.9-1.1: 1.9-2.0.

[0018] A capillary gas chromatography column, the stationary phase of the capillary gas chromatography column is an alkyl-functionalized cyclotriveratrylene.

[0019] As a further optimization of the above technical solution, the preparation method of the capillary gas chromatography column is the static coating method.

[0020] Application of a capillary gas chromatography column in separating benzene series, homologues, dimethylnaphthalene isomers, dibromobenzene isomers, dichlorobenzene isomers, chloronitrobenzene isomers, dimethylaniline isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, hydroxybenzaldehyde isomers, benzenediol isomers, phenylenediamine isomers, 7 groups of cis-trans isomers or 22-component complex mixtures. The benzene series includes toluene, ethylbenzene, isopropylbenzene, propylbenzene, sec-butylbenzene and butylbenzene;

[0021] The homologues include bromododecane, bromoundecane, bromodecane, bromononane, bromooctane, bromoheptane, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate and methyl dodecanoate;

[0022] The dimethylnaphthalene isomers include 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene and 1,2-dimethylnaphthalene;

[0023] The dibromobenzene isomers include o-dibromobenzene, m-dibromobenzene and p-dibromobenzene;

[0024] The dichlorobenzene isomers include o-dichlorobenzene, m-dichlorobenzene and p-dichlorobenzene;

[0025] The chloronitrobenzene isomers include o-chloronitrobenzene, m-chloronitrobenzene and p-chloronitrobenzene;

[0026] The dimethylaniline isomers include 2,6-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline and 2,3-dimethylaniline;

[0027] The bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde;

[0028] The nitrobenzaldehyde isomers include o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-nitrobenzaldehyde;

[0029] The hydroxybenzaldehyde isomers include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde;

[0030] The benzenediol isomers include o-benzenediol, p-benzenediol and m-benzenediol;

[0031] The phenylenediamine isomers include o-phenylenediamine, p-phenylenediamine and m-phenylenediamine;

[0032] The 7 sets of cis-trans isomers include cis-1,3-dichloropropene and trans-1,3-dichloropropene, cis-2-butenenitrile and trans-2-butenenitrile, cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-nerolidol and trans-nerolidol, cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate, cis-dimethyl citrate acetal and trans-dimethyl citrate acetal;

[0033] The 22-component complex mixture is a mixture of ethylbenzene, hexanol, bromohexane, decane, octanone, 1,2,4-trimethylbenzene, bromoheptane, nonanone, iodobenzene, dodecane, nonanol, 4-methylphenol, tridecane, decanol, 4-ethylphenol, 4-chloronitrobenzene, 2-methylnaphthalene, 1-methylnaphthalene, pentadecane, methyl dodecanoate, n-hexadecane and 3-iodoaniline.

[0034] Application of a capillary gas chromatography column in detecting the concentrations of isopropylbenzene, cis-decalin and geraniol.

[0035] Compared with the prior art, the present invention has the following beneficial effects.

[0036] The alkyl-functionalized cyclotriveratrylene prepared by the present invention has a unique C 3 symmetric structure and alkoxy chain functional groups, and has a variety of different weak interaction forces with different analytes, including: van der Waals force, hydrogen bond, π-π interaction, dipole-dipole interaction, etc., making the capillary gas chromatography column prepared with the alkyl-functionalized cyclotriveratrylene as the stationary phase have good separation performance;

[0037] The alkyl-functionalized cyclotriveratrylene prepared by the present invention combines the structural characteristics of cyclotriveratrylene and the advantages of alkyl functionalization. By introducing a long alkyl chain at the lower edge of cyclotriveratrylene, the properties of cyclotriveratrylene as the stationary phase of the capillary gas chromatography column are improved. Compared with ordinary cyclotriveratrylene, the melting point of the alkyl-functionalized cyclotriveratrylene prepared by the present invention is reduced, the film-forming property and thermal stability are improved, and the separation performance of cyclotriveratrylene as the stationary phase for analytes is also improved, and it can effectively separate benzene series, homologues, dimethylnaphthalene isomers, dibromobenzene isomers, dichlorobenzene isomers, chloronitrobenzene isomers, dimethylaniline isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, hydroxybenzaldehyde isomers, benzenediol isomers, phenylenediamine isomers, 7 sets of cis-trans isomers or 22-component complex mixture. Description of the Drawings

[0038] Figure 1 is a reaction diagram of the preparation of alkyl-functionalized cyclotriveratrylene from 1,2-dihydroxybenzene as a raw material in the present invention;

[0039] Figure 2 is the thermogravimetric graph of alkyl-functionalized cyclotriveratrylene;

[0040] Figure 3 is the column efficiency graph of the capillary gas chromatographic column prepared by the present invention measured at 120 °C with dodecane as the analyte;

[0041] Figure 4 is the chromatogram of the separation of benzene series and various homologues by the capillary gas chromatographic column prepared by the present invention, wherein the benzene series includes toluene, ethylbenzene, isopropylbenzene, propylbenzene, sec-butylbenzene and butylbenzene; various homologues include bromododecane, bromoundecane, bromodecane, bromononane, bromooctane, bromoheptane, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate and methyl dodecanoate;

[0042] Figure 5 is the chromatogram of the separation of position isomers with different substituents by the capillary gas chromatographic column prepared by the present invention, including: 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene, 1,2-dimethylnaphthalene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, 2,6-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline, 2,3-dimethylaniline, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, catechol, hydroquinone, resorcinol, o-phenylenediamine, p-phenylenediamine, m-phenylenediamine;

[0043] Figure 6 is the chromatogram of the separation of benzaldehyde isomers substituted with different groups by the capillary gas chromatographic column prepared by the present invention and the separation comparison with commercial columns HP-5 and HP-35, including bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde;

[0044] Figure 7It is the chromatogram of separating halo - benzene isomers substituted by different groups with the capillary gas chromatography column prepared by the present invention and compared with the commercial columns HP - 5 and HP - 35. It includes dibromo - benzene isomers: o - dibromobenzene, m - dibromobenzene, p - dibromobenzene, dichlorobenzene isomers: o - dichlorobenzene, m - dichlorobenzene, p - dichlorobenzene, and chloronitro - benzene isomers: o - chloronitrobenzene, m - chloronitrobenzene, p - chloronitrobenzene;

[0045] Figure 8 It is the chromatogram of separating 7 groups of cis - trans isomers with different polarities with the capillary gas chromatography column prepared by the present invention. Among them, (a): cis - 1,3 - dichloropropene, trans - 1,3 - dichloropropene, (b): cis - 2 - butenenitrile, trans - 2 - butenenitrile, (c): cis - 4 - methyl - 2 - (2 - methyl - 1 - propenyl)tetrahydropyran, trans - 4 - methyl - 2 - (2 - methyl - 1 - propenyl)tetrahydropyran, (d): cis - 4 - tert - butylcyclohexanol, trans - 4 - tert - butylcyclohexanol, (e): cis - nerolidol, trans - nerolidol, (f): cis - methyl dihydrojasmonate, trans - methyl dihydrojasmonate, (g): cis - dimethyl citrate acetal, trans - dimethyl citrate acetal;

[0046] Figure 9 It is the chromatogram of separating a 22 - component complex mixture sample with different polarities and different types with the capillary gas chromatography column prepared by the present invention. The 22 - component complex mixture is as follows: 1: ethylbenzene, 2: hexanol, 3: bromohexane, 4: decane, 5: octanone, 6: 1,2,4 - trimethylbenzene, 7: bromoheptane, 8: nonanone, 9: iodobenzene, 10: dodecane, 11: nonanol, 12: 4 - methylphenol, 13: tridecane, 14: decanol, 15: 4 - ethylphenol, 16: 4 - chloronitrobenzene, 17: 2 - methylnaphthalene, 18: 1 - methylnaphthalene, 19: pentadecane, 20: methyl dodecanoate, 21: n - hexadecane, 22: 3 - iodoaniline;

[0047] Figure 10 It is the chromatogram of separating chloronitro - benzene isomers with the capillary gas chromatography column prepared by the present invention and compared with the capillary gas chromatography column prepared with ordinary cyclotriveratrylene as the stationary phase and the capillary gas chromatography column prepared with alkyl - functionalized pillar[6]arene as the stationary phase. In the figure, CTV - C10 is the capillary gas chromatography column prepared by the present invention, CTV is the capillary gas chromatography column prepared with ordinary cyclotriveratrylene as the stationary phase, and P6A - C10 is the capillary gas chromatography column prepared with alkyl - functionalized pillar[6]arene as the stationary phase;

[0048] Figure 11It is a chromatogram of separating hydroquinone isomers by the capillary gas chromatography column prepared in the present invention, with the capillary gas chromatography columns prepared by using ordinary cyclotriveratrylene as the stationary phase and the capillary gas chromatography column prepared by using alkyl-functionalized column hexarene as the stationary phase for comparison; in the figure, CTV-C10 is the capillary gas chromatography column prepared in the present invention, CTV is the capillary gas chromatography column prepared by using ordinary cyclotriveratrylene as the stationary phase, and P6A-C10 is the capillary gas chromatography column prepared by using alkyl-functionalized column hexarene as the stationary phase;

[0049] Figure 12 It is a chromatogram of separating phenylenediamine isomers by the capillary gas chromatography column prepared in the present invention, with the capillary gas chromatography columns prepared by using ordinary cyclotriveratrylene as the stationary phase and the capillary gas chromatography column prepared by using alkyl-functionalized column hexarene as the stationary phase for comparison; in the figure, CTV-C10 is the capillary gas chromatography column prepared in the present invention, CTV is the capillary gas chromatography column prepared by using ordinary cyclotriveratrylene as the stationary phase, and P6A-C10 is the capillary gas chromatography column prepared by using alkyl-functionalized column hexarene as the stationary phase;

[0050] Figure 13 It is a chromatogram of detecting three actual samples by the capillary gas chromatography column prepared in the present invention. The three actual samples include cumene actual sample, cis-decalin actual sample and geraniol actual sample. Detailed implementation manners

[0051] The technical solutions of the present invention will be further elaborated in detail below in combination with specific embodiments. For the parts not detailedly recorded and disclosed in the following embodiments of the present invention, they should all be understood as the prior art known or should be known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are the conventional reagents, methods and equipment in the technical field; unless otherwise specified, the reagents and materials used in the present invention are all commercially available.

[0052] As Figure 1 shown, the present invention uses 1,2-dihydroxybenzene as the raw material. First, intermediate I is obtained through an etherification reaction. Secondly, intermediate I undergoes a cyclization reaction to obtain alkyl-functionalized cyclotriveratrylene, named CTV-C10.

[0053] During the whole experimental operation process of preparing alkyl-functionalized cyclotriveratrylene, the reaction conditions are mild, the cost is low, and the steps are few. The structure of this alkyl-functionalized cyclotriveratrylene is novel, and the stability performance shown is good, and it has a good separation effect on the analytes.

[0054] The alkyl-functionalized cyclotriveratrylene CTV-C10 prepared by the present invention combines the structural characteristics of cyclotriveratrylene and the advantages of alkyl functionalization. Among them, cyclotriveratrylene has the advantages of being easy to chemically modify, high chemical stability, a unique C 3 symmetrical structure and an electron-rich cavity, etc. Moreover, cyclotriveratrylene is easy to derivatize, and introducing a non-polar long alkyl chain can improve the properties of cyclotriveratrylene as a stationary phase for capillary gas chromatography columns, which can reduce the melting point of cyclotriveratrylene, improve the film-forming property, thermal stability of cyclotriveratrylene, and the separation performance of cyclotriveratrylene as a chromatographic stationary phase for analytes.

[0055] First, the inner surface of the capillary column is roughened by the traditional sodium chloride microcrystal deposition method for chromatographic column pretreatment. Secondly, the column is prepared by the static coating method to uniformly disperse the stationary liquid on the inner wall of the capillary column. Finally, the coated capillary gas chromatography column is aged by a programmed temperature method under nitrogen protection, that is, the preparation of the capillary gas chromatography column is completed, and the stationary phase on the prepared capillary gas chromatography column is uniformly coated.

[0056] The capillary gas chromatography column prepared by the present invention has good separation performance for different analytes, and can separate benzene series, homologues, dimethylnaphthalene isomers, dibromobenzene isomers, dichlorobenzene isomers, chloronitrobenzene isomers, dimethylaniline isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, hydroxybenzaldehyde isomers, benzenediol isomers, phenylenediamine isomers, 7 groups of cis-trans isomers, 22-component complex mixtures, etc.

[0057] By using CTV-C10 as the stationary phase of the capillary gas chromatography column, the present invention combines the structural characteristics of cyclotriveratrylene and the advantages of alkyl functionalization, making it a reality for this new material to be used as the stationary phase of the capillary gas chromatography column, and providing a richer separation material for the research of chromatographic separation.

[0058] Example 1

[0059] A preparation method of an alkyl-functionalized cyclotriveratrylene, comprising the following steps:

[0060] S1. React 1.00 g (9.08 mmol) of 1,2-dihydroxybenzene, 6.03 g (27.26 mmol) of 1-bromodecane, 5.04 g (36.47 mmol) of potassium carbonate and 40 mL of N,N-dimethylformamide at 60 °C for 23 h, let it stand and cool to 25 °C, concentrate the solvent under reduced pressure to dryness, wash with deionized water and then perform suction filtration, dry the filter cake to obtain a crude product, dissolve the crude product in dichloromethane and then perform suction filtration, and evaporate the filtrate to dryness to obtain 2.89 g of a yellowish-white solid intermediate I. The chemical structural formula of intermediate I is .

[0061] The characterization data of Intermediate I are as follows: m.p. 40.1 - 40.7 °C. 1 H NMR (400 MHz, CDCl 3 ) δ: 6.89 (s, 4H), 3.99 (t, J = 6.6 Hz, 4H), 1.81 (p, J = 6.9 Hz, 4H), 1.46 (q, J = 7.3 Hz, 4H), 1.37 - 1.28 (m, 24H), 0.88 (t, J = 6.6 Hz, 6H). IR (KBr, cm -1 ) : 1051.82 (C - O - C), 1222.43 (C - O - C), 1455.16 (C = C), 1463.69 (C = C), 1474.06 (C = C), 2849.08 (CH 2 ), 2956.16 (CH 3 ).

[0062] S2. Add 1.00 g (2.56 mmol) of Intermediate I, 0.08 g (2.66 mmol) of paraformaldehyde, and 15 mL of glacial acetic acid obtained in Step S1 to a 50 - mL single - necked flask, react at 0 °C for 20 min, add 0.50 g (5.12 mmol) of concentrated sulfuric acid, react at 30 °C for 5 h, add an aqueous sodium hydroxide solution to quench the reaction, wash the organic phase with saturated sodium chloride solution, filter by suction, evaporate to dryness to obtain 1.12 g of crude product, and perform column chromatography purification. The eluent is petroleum ether:dichloromethane = 5:1 (V:V) to obtain 0.14 g of the final product II in the form of a yellow paste. The final product II is CTV - C10.

[0063] The characterization data of the final product II are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ: 6.82 (s, 6H), 4.72 - 4.68 (s, 3H), 3.99 - 3.86 (m, 12H), 3.50 - 3.47 (s, 3H), 1.76 (p, J = 6.8 Hz, 12H), 1.45 - 1.37 (m, 12H), 1.25 - 1.33 (m, 72H), 0.87 (t, J = 6.7 Hz, 18H). IR (KBr, cm -1 ) : 1051.82 (C - O - C), 1392.04 (C - O - C), 1426.04 (C = C), 1455.16 (C = C), 1463.69 (C = C), 2849.08 (CH 2) ,2918.20(CH 2 )。

[0064] Example 2

[0065] The difference between this example and Example 1 is: different reaction conditions.

[0066] S1. React 1.50 g (13.62 mmol) of 1,2-dihydroxybenzene, 8.80 g (39.79 mmol) of 1-bromodecane, 7.45 g (53.91 mmol) of potassium carbonate and 40 mL of N,N-dimethylformamide at 63 °C for 23.5 h. Let it stand and cool to 25 °C. Concentrate the solvent under reduced pressure to dryness. Wash with deionized water and then perform suction filtration. Dry the filter cake to obtain the crude product. Dissolve the crude product in dichloromethane and then perform suction filtration. Evaporate the filtrate to dryness to obtain 4.03 g of a yellowish-white solid intermediate Ⅰ.

[0067] S2. Add 1.60 g (4.10 mmol) of intermediate Ⅰ obtained in step S1, 0.13 g (4.32 mmol) of paraformaldehyde and 20 mL of glacial acetic acid to a 50 mL single-necked flask. React at 0 °C for 20 min. Add 0.80 g (8.16 mmol) of concentrated sulfuric acid and react at 27 °C for 5.5 h. Quench the reaction with an aqueous sodium hydroxide solution. Wash the organic phase with saturated sodium chloride solution, perform suction filtration, and evaporate to dryness to obtain 1.71 g of a crude product. Purify it by column chromatography. The eluent is petroleum ether:dichloromethane = 5:1 (V:V) to obtain 0.33 g of a yellow paste-like final product Ⅱ. The final product Ⅱ is CTV-C10.

[0068] Example 3

[0069] The difference between this example and Example 1 is: different reaction conditions.

[0070] S1. React 2.00 g (18.16 mmol) of 1,2-dihydroxybenzene, 12.05 g (54.48 mmol) of 1-bromodecane, 10.04 g (72.65 mmol) of potassium carbonate and 40 mL of N,N-dimethylformamide at 65 °C for 24 h. Let it stand and cool to 25 °C. Concentrate the solvent under reduced pressure to dryness. Wash with deionized water and then perform suction filtration. Dry the filter cake to obtain the crude product. Dissolve the crude product in dichloromethane and then perform suction filtration. Evaporate the filtrate to dryness to obtain 6.01 g of a yellowish-white solid intermediate Ⅰ.

[0071] S2. Add 2 g (5.12 mmol) of Intermediate I obtained in Step S1, 0.15 g (5.00 mmol) of paraformaldehyde, and 20 mL of glacial acetic acid into a 50 mL single-necked flask, react at 0 °C for 20 min, add 1.00 g (10.20 mmol) of concentrated sulfuric acid, react at 25 °C for 6 h, quench the reaction with an aqueous sodium hydroxide solution, wash the organic phase with saturated sodium chloride solution, filter by suction, evaporate to dryness to obtain 2.17 g of crude product, and perform column chromatography purification. The eluent is petroleum ether:dichloromethane = 5:1 (V:V) to obtain 0.45 g of the final product II in the form of a yellow paste. The final product II is CTV-C10.

[0072] Example 4

[0073] Preparation of the capillary gas chromatography column of the present invention:

[0074] (1) Cut a quartz capillary with a length of 5 m and an inner diameter of 250 μm. First, rinse it with dichloromethane for 10 min, and then age it at 200 °C for 2 - 3 h under nitrogen protection, so that the impurities in the capillary column flow out with nitrogen at high temperature.

[0075] (2) Weigh 1.31 g of ground NaCl powder, place it in 10 mL of anhydrous methanol solution, stir vigorously for 45 min to obtain a saturated sodium chloride methanol solution. Take 6 mL of the saturated solution and add it to 8 mL of dichloromethane solution under strong stirring, then add 0.6 mL of anhydrous methanol solution, stir for 5 min, and then add 8 mL of dichloromethane solution and continue to stir for 2 min to obtain a saturated colloidal solution. Complete the roughening of the inner surface of the capillary column.

[0076] (3) Under a nitrogen pressure of 0.2 MPa, press this saturated colloidal solution into the capillary, and then blow out the solution in the column with nitrogen. Under nitrogen protection, recrystallize at 200 °C for 3 h.

[0077] (4) In this experiment, the static method is used to prepare the column. Dissolve the CTV-C10 prepared in Example 1 in dichloromethane solution to prepare a stationary liquid with a concentration of 0.15% (w / v), and perform ultrasonic treatment for 5 min to remove the bubbles in the stationary liquid.

[0078] (5) Use a syringe to push the stationary liquid into the capillary gas chromatography column until the stationary liquid fills the entire column. Then seal one end of the capillary and connect the other end to a vacuum system. Slowly evaporate the solvent in a 38 °C constant temperature water bath, and the stationary liquid can be evenly dispersed on the inner wall of the capillary column.

[0079] (6) Under nitrogen protection, age the coated capillary gas chromatography column by the method of programmed temperature rise: maintain at 40 °C for 30 min, then rise to 180 °C at a rate of 1 °C / min, and maintain for 7 h to complete the aging of the chromatography column and obtain the capillary gas chromatography column.

[0080] 1. Thermogravimetric Diagram of Alkyl-Functionalized Cyclotriveratrylene Stationary Phase

[0081] As Figure 2 shown in the thermogravimetric diagram of alkyl-functionalized cyclotriveratrylene, in this invention, CTV-C10 is used as the stationary phase of the capillary gas chromatography column. At 295 °C, the weight loss is 5%, indicating good thermal stability up to 295 °C.

[0082] Meanwhile, the melting point of ordinary cyclotriveratrylene without any modification is 230 °C, and it is a white solid at room temperature. The CTV-C10 prepared in this invention is in paste form at room temperature, indicating that the melting point of CTV-C10 is lower than that of ordinary cyclotriveratrylene.

[0083] 2. Separation Effect Examples of the Capillary Gas Chromatography Column Prepared in Example 4

[0084] <Determination of n-Dodecane>

[0085] As Figure 3 shown, the Golay curve of n-dodecane was determined using the capillary gas chromatography column prepared in Example 4. The specific chromatographic conditions are: column oven temperature 120 °C, carrier gas: nitrogen, carrier gas flow rate: 21.19 cm / s, and the lowest theoretical plate height is: 0.29 mm.

[0086] It can be seen that the capillary gas chromatography column prepared by the static coating method in this invention has high column efficiency.

[0087] <Separation of Benzene Series Compounds and Various Homologues>

[0088] Different benzene series compounds were selected as analytes, including toluene, ethylbenzene, isopropylbenzene, propylbenzene, sec-butylbenzene, and butylbenzene;

[0089] Various homologues were selected as analytes, including dodecyl bromide, undecyl bromide, decyl bromide, nonyl bromide, octyl bromide, heptyl bromide, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, and methyl dodecanoate.

[0090] Chromatographic separation conditions: maintain at 40 °C for 1 min, then increase the temperature to 160 °C at a rate of 10 °C / min, and the carrier gas flow rate is 0.6 mL / min.

[0091] Figure 4It is the chromatogram of the separation of benzene series and various homologues by a capillary gas chromatography column. It can be seen that the capillary gas chromatography column prepared by the present invention can separate the above-mentioned benzene series and various homologues.

[0092] As Figure 4 shown, the symmetry factor ranges of mixed alcohols and mixed aldehydes among homologues are between 0.95 and 1.05, and the chromatographic peak shapes are symmetrical and sharp, proving that the stationary phase is evenly coated on the inner wall of the capillary gas chromatography column and has good film-forming properties.

[0093] <Separation of positional isomers substituted with different groups>

[0094] Select positional isomers substituted with different groups as analytes, including 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene, 1,2-dimethylnaphthalene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, 2,6-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline, 2,3-dimethylaniline, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-benzenediol, p-benzenediol, m-benzenediol, o-phenylenediamine, p-phenylenediamine and m-phenylenediamine.

[0095] Chromatographic separation conditions: maintain at 40 °C for 1 min, increase the temperature to 160 °C at a rate of 10 °C / min, and the carrier gas flow rate is 0.6 mL / min.

[0096] Figure 5 It is the chromatogram of the separation of positional isomers substituted with different groups. It can be seen that the capillary gas chromatography column prepared by the present invention can separate positional isomers substituted with different groups.

[0097] <Separation of benzaldehyde isomers substituted with different groups>

[0098] Select benzaldehyde isomers substituted with different groups as analytes, including bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, and nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde.

[0099] Chromatographic separation conditions: maintain at 40 °C for 1 min, increase the temperature to 160 °C at a rate of 10 °C / min, and the carrier gas flow rate is 0.6 mL / min.

[0100] Figure 6 It is the chromatogram of the separation of benzaldehyde isomers substituted with different groups by the capillary gas chromatography column and the separation comparison with commercial columns HP-5 and HP-35, and the effect is better than that of the polysiloxane commercial columns HP-5 and HP-35.

[0101] <Separation of halogenated benzene isomers substituted with different groups>

[0102] Select halogenated benzene isomers substituted with different groups as analytes, including dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene.

[0103] Chromatographic separation conditions: Hold at 40 °C for 1 min, increase the temperature to 160 °C at a heating rate of 10 °C / min, and the carrier gas flow rate is 0.6 mL / min.

[0104] Figure 7 It is the chromatogram of separating halogenated benzene isomers substituted with different groups by the capillary gas chromatographic column prepared in the example and comparing with the commercial columns HP-5 and HP-35. As Figure 7 shown, the capillary gas chromatographic column prepared in the example can effectively separate halogenated benzene isomers substituted with different groups, and the effect is better than that of the polysiloxane commercial columns HP-5 and HP-35.

[0105] <Separation of 7 groups of cis-trans isomers>

[0106] Select 7 groups of cis-trans isomers as analytes. The 7 groups of cis-trans isomers include cis-1,3-dichloropropene and trans-1,3-dichloropropene, cis-2-butenenitrile and trans-2-butenenitrile, cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-nerolidol and trans-nerolidol, cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate, cis-dimethyl citrate acetal and trans-dimethyl citrate acetal; Use the capillary gas chromatographic column prepared in the example to separate the above 7 groups of cis-trans isomers.

[0107] Chromatographic separation conditions: Hold at 40 °C for 1 min, increase the temperature to 160 °C at a heating rate of 10 °C / min, and the carrier gas flow rate is 0.6 mL / min.

[0108] Figure 8It is the chromatogram of separating 7 groups of cis-trans isomers with different polarities by the capillary gas chromatography column prepared in the example. Among them, (a): cis-1,3-dichloropropene and trans-1,3-dichloropropene; (b): cis-2-butenenitrile and trans-2-butenenitrile; (c): cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran; (d): cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol; (e): cis-nerolidol and trans-nerolidol; (f): cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate; (g): cis-dimethyl citrate acetal and trans-dimethyl citrate acetal.

[0109] As Figure 8 shown, the capillary gas chromatography column prepared in the example can completely separate each group of cis-trans isomers, demonstrating the advantage of CTV-C10 as the stationary phase for separating cis-trans isomers, with fast and efficient separation.

[0110] <Separation of 22-component complex mixture>

[0111] Select a 22-component complex mixture as the analyte. The 22-component complex mixture is a mixture of ethylbenzene, hexanol, bromohexane, decane, octanone, 1,2,4-trimethylbenzene, bromoheptane, nonanone, iodobenzene, dodecane, nonanol, 4-methylphenol, tridecane, decanol, 4-ethylphenol, 4-chloronitrobenzene, 2-methylnaphthalene, 1-methylnaphthalene, pentadecane, methyl dodecanoate, n-hexadecane, and 3-iodoaniline. Use the capillary gas chromatography column prepared in the example to separate the 22-component complex mixture.

[0112] Chromatographic separation conditions: Hold at 40°C for 1 min, increase the temperature to 160°C at a rate of 10°C / min, and the carrier gas flow rate is 0.6 mL / min.

[0113] Figure 9 It is the chromatogram of separating the 22-component complex mixture by the capillary gas chromatography column. Among them, 1: ethylbenzene, 2: hexanol, 3: bromohexane, 4: decane, 5: octanone, 6: 1,2,4-trimethylbenzene, 7: bromoheptane, 8: nonanone, 9: iodobenzene, 10: dodecane, 11: nonanol, 12: 4-methylphenol, 13: tridecane, 14: decanol, 15: 4-ethylphenol, 16: 4-chloronitrobenzene, 17: 2-methylnaphthalene, 18: 1-methylnaphthalene, 19: pentadecane, 20: methyl dodecanoate, 21: n-hexadecane, 22: 3-iodoaniline.

[0114] As Figure 9As shown, the capillary gas chromatography column prepared by the example has a good separation effect on a 22-component complex mixture, with a relatively large number of analytes and a wide polarity range. It demonstrates the good characteristics of CTV-C10 as a stationary phase for separating complex mixtures.

[0115] <Separation of chloronitrobenzene isomers>

[0116] The capillary gas chromatography column CTV-C10 prepared in Example 4, the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene, and the capillary gas chromatography column P6A-C10 prepared with alkyl-functionalized column hexarene were used to separate chloronitrobenzene isomers, including o-chloronitrobenzene, m-chloronitrobenzene, and p-chloronitrobenzene.

[0117] Chromatographic separation conditions: Hold at 40 °C for 1 min, increase the temperature to 160 °C at a rate of 10 °C / min, and the carrier gas flow rate is 0.6 mL / min.

[0118] It can be seen from Figure 10 that the capillary gas chromatography column CTV-C10 prepared in Example 4 can separate chloronitrobenzene isomers, and the effect is better than that of the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene as the stationary phase and the capillary gas chromatography column P6A-C10 prepared with alkyl-functionalized column hexarene.

[0119] <Separation of benzenediol isomers>

[0120] The capillary gas chromatography column CTV-C10 prepared in Example 4, the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene, and the capillary gas chromatography column P6A-C10 prepared with alkyl-functionalized column hexarene were used to separate benzenediol isomers, including catechol, resorcinol, and hydroquinone.

[0121] Chromatographic separation conditions: Hold at 40 °C for 1 min, increase the temperature to 160 °C at a rate of 10 °C / min, and the carrier gas flow rate is 0.6 mL / min.

[0122] It can be seen from Figure 11 that the capillary gas chromatography column CTV-C10 prepared in Example 4 can separate benzenediol isomers, and the effect is better than that of the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene as the stationary phase and the capillary gas chromatography column P6A-C10 prepared with alkyl-functionalized column hexarene. When the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene as the stationary phase was used to separate benzenediol isomers, the analyte was not eluted, indicating that the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene as the stationary phase could not separate benzenediol isomers.

[0123] <Separation of phenylenediamine isomers>

[0124] The capillary gas chromatography column CTV-C10 prepared in Example 4, the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene, and the capillary gas chromatography column P6A-C10 prepared with alkyl-functionalized column hexaphenylene were used to separate phenylenediamine isomers, which include o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.

[0125] Chromatographic separation conditions: Maintain at 40°C for 1 min, increase the temperature to 160°C at a rate of 10°C / min, and the carrier gas flow rate is 0.6 mL / min.

[0126] It can be seen from Figure 12 that the capillary gas chromatography column CTV-C10 prepared in Example 4 can separate phenylenediamine isomers, and the effect is better than that of the capillary gas chromatography column CTV prepared with ordinary cyclotriveratrylene as the stationary phase and the capillary gas chromatography column P6A-C10 prepared with alkyl-functionalized column hexaphenylene. Among them, when using the capillary gas chromatography column P6A-C10 prepared with alkyl-functionalized column hexaphenylene to separate phenylenediamine isomers, the analytes were not eluted because the alkyl-functionalized column hexaphenylene has too strong an adsorption property for phenylenediamine isomers, resulting in the inability to separate phenylenediamine isomers.

[0127] III. Detection of three actual samples

[0128] Three actual samples were selected as analytes and detected using the capillary gas chromatography column prepared in the example. Chromatographic separation conditions: Maintain at 40°C for 1 min, increase the temperature to 160°C at a rate of 10°C / min, and the carrier gas flow rate is 0.6 mL / min.

[0129] Figure 13 is the chromatogram of the capillary gas chromatography column detecting 3 actual samples, including cumene actual sample, cis-decalin actual sample, and geraniol actual sample. As Figure 13 shown, the capillary gas chromatography column prepared through the example can detect isomeric impurities in 3 actual samples. As can be seen from Table 1, the content of the actual samples was calculated using the peak area normalization method, and the tested actual samples are consistent with the purity on their labels.

[0130] Table 1

[0131] Actual sample Label purity (%) Test purity (%) Isomer impurity Impurity content (%) Cumene 99.00 99.07 n-Propylbenzene 0.17 Cis-decalin 98.00 97.63 Trans-decalin 1.17 Geraniol 97.00 97.29 Nerol 0.67

[0132] The above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should all be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claimed rights.

Claims

1. A capillary gas chromatography column, characterized in that: The stationary phase of the capillary gas chromatography column is alkyl-functionalized cyclotriveratrol, and the chemical structural formula of alkyl-functionalized cyclotriveratrol is ; The preparation method of the capillary gas chromatographic column is a static coating method.

2. A capillary gas chromatography column as claimed in claim 1, characterized in that: The preparation method of alkyl-functionalized cyclotriveratrol comprises the following steps: S1. Take 1,2-dihydroxybenzene, 1-bromodecane, potassium carbonate and N,N-dimethylformamide for etherification reaction to obtain intermediate I. The chemical structure of intermediate I is ; S2. Take the intermediate I, paraformaldehyde, sulfuric acid and glacial acetic acid to carry out a cyclization reaction. After the reaction is completed, the alkyl-functionalized cyclotriveratrol is obtained by post-treatment and purification.

3. A capillary gas chromatography column as claimed in claim 2, characterized in that: The temperature of the etherification reaction is 60-65°C, the reaction time is 23-24h, and after the reaction is completed, the temperature is lowered to 25°C. The reaction product is purified by column chromatography using dichloromethane as an eluent to obtain intermediate I.

4. A capillary gas chromatography column as claimed in claim 2, characterized in that: In step S1, the molar ratio of 1,2-dihydroxybenzene, 1-bromodecane and potassium carbonate is 1.0:2.9~3.0:3.9~4.

0.

5. A capillary gas chromatography column as claimed in claim 2, characterized in that: The reaction temperature of the cyclization reaction is 25-30° C., the reaction time is 5-6 h, and the reaction product is purified by column chromatography, and the volume ratio of petroleum ether and dichloromethane in the eluent is 5:

1.

6. A capillary gas chromatography column as claimed in claim 2, characterized in that: In step S2, the molar ratio of intermediate I, paraformaldehyde and sulfuric acid is 1.0:0.9~1.1:1.9~2.

0.

7. Use of the capillary gas chromatography column as claimed in claim 1 in separating benzene series, homologues, dimethylnaphthalene isomers, dibromobenzene isomers, dichlorobenzene isomers, chloronitrobenzene isomers, dimethylaniline isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, hydroxybenzaldehyde isomers, hydroquinone isomers, phenylenediamine isomers, 7 groups of cis-trans isomers or 22-component complex mixtures, characterized in that: BTEX includes toluene, ethylbenzene, cumene, propylbenzene, sec-butylbenzene and butylbenzene; Homologs include dodecane bromide, undecane bromide, decane bromide, nonane bromide, octane bromide, heptane bromide, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, valeraldehyde, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, and methyl dodecanoate; Dimethylnaphthalene isomers include 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene and 1,2-dimethylnaphthalene; Dibromobenzene isomers include o-dibromobenzene, m-dibromobenzene and p-dibromobenzene; Dichlorobenzene isomers include o-dichlorobenzene, m-dichlorobenzene and p-dichlorobenzene; Chloronitrobenzene isomers include o-chloronitrobenzene, m-chloronitrobenzene and p-chloronitrobenzene; Dimethylaniline isomers include 2,6-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline and 2,3-dimethylaniline; Bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde; Nitrobenzaldehyde isomers include o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde; Hydroxybenzaldehyde isomers include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde; The isomers of catechol include catechol, hydroquinone and resorcinol; Phenylenediamine isomers include o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine; 7 groups of cis-trans isomers include cis-1,3-dichloropropene and trans-1,3-dichloropropene, cis-2-butenenitrile and trans-2-butenenitrile, cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-nerolidol and trans-nerolidol, cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate, cis-citric acid dimethyl acetal and trans-citric acid dimethyl acetal; The 22-component complex mixture is a mixture of ethylbenzene, hexanol, hexyl bromide, decane, octanone, 1,2,4-trimethylbenzene, heptane bromide, nonanone, iodobenzene, dodecane, nonanol, 4-methylphenol, tridecane, decanol, 4-ethylphenol, 4-chloronitrobenzene, 2-methylnaphthalene, 1-methylnaphthalene, pentadecane, methyl dodecanoate, n-hexadecane, and 3-iodoaniline.

8. Use of the capillary gas chromatography column as claimed in claim 1 in detecting the concentrations of isopropylbenzene, cis-decalin and geraniol.

Images