Ester group functionalized cyclotriveratrum hydrocarbon as well as preparation method and application thereof

Abstract

The invention provides ester group functionalized cyclotriveratrum hydrocarbon as well as a preparation method and application thereof, and relates to the technical field of gas chromatographic analys.According to the ester group functionalized cyclotriveratrum hydrocarbon and the preparation method and application thereof, a long alkyl chain and an ester group are introduced to the lower edge of cyclotriveratrum hydrocarbon, so that the property of the cyclotriveratrum hydrocarbon serving as a gas chromatographic stationary phase is improved; by introducing a non-polar alkyl chain and a polar ester group, the melting point of the cyclotriveratrum hydrocarbon can be reduced, the film-forming property and the thermal stability of the cyclotriveratrum hydrocarbon are improved, and the separation performance of the cyclotriveratrum hydrocarbon serving as a stationary phase of a capillary gas chromatographic column on an analyte is improved; the method can effectively separate methyl benzaldehyde isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, diethylbenzene isomers, benzene series, homologues, cis-trans isomers and multi-component complex mixtures.

Description

Technical Field

[0001] The present invention relates to the technical field of gas chromatography analysis, and specifically relates to an ester-functionalized cyclotriveratrylene, a preparation method thereof, and an application of the cyclotriveratrylene in a capillary gas chromatography column. 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 qualitative and quantitative analysis of volatile organic compounds. For non-volatile liquids and solids, they can be analyzed after high-temperature pyrolysis and gasification. Gas chromatography can be used in combination with infrared absorption spectrometry or mass spectrometry as a means of separating complex samples to achieve higher 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 stationary phase materials such as polysiloxanes and polyethylene glycols can already achieve good separation of most substances. However, when it comes to separating some mixtures with extremely close boiling points and polarities, or positional isomers and cis-trans isomers, the available materials are still very limited. Therefore, new capillary gas chromatography column 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 paper "Research on the Separation Performance and Application of Novel Gas Chromatography Stationary Phases of Cyclotriveratrylene and Triphenylene Indene (Lv Qing, Beijing Institute of Technology, June 2016).

[0006] Reference 1 discloses that the CTV (Chinese name: 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 methylbenzaldehyde isomers.

[0007] Reference 2: Chinese patent document with publication number CN 117563572 A.

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

[0009] The present invention aims to provide an ester-functionalized cyclotriveratrylene, a preparation method thereof, and an application of the cyclotriveratrylene in a capillary gas chromatography column, so as to solve the problem of poor separation effect of methylbenzaldehyde isomers by macrocyclic compounds in the prior art.

[0010] To achieve the above object, the specific solution adopted by the present invention is as follows: In the first aspect of the present invention, an ester-functionalized cyclotriveratrylene is proposed, and the chemical structural formula of the ester-functionalized cyclotriveratrylene is: .

[0011] In the second aspect of the present invention, a preparation method of the above ester-functionalized cyclotriveratrylene is proposed, which includes the following steps: S1. Take 1,2-dihydroxybenzene, 1,10-dibromodecane, potassium carbonate, and N,N-dimethylformamide for an etherification reaction to obtain intermediate I, and the chemical structural formula of intermediate I is ; S2. Take intermediate I obtained in step S1, paraformaldehyde, sulfuric acid, and glacial acetic acid for a cyclization reaction to obtain intermediate II, and the chemical structural formula of intermediate II is ; S3. Take intermediate II obtained in step S2, potassium acetate, and N,N-dimethylformamide for a substitution reaction, and purify the product after the substitution reaction is completed, thus obtaining the ester-functionalized cyclotriveratrylene.

[0012] As a further optimization of the above technical solution, in step S1, the temperature of the etherification reaction is 60-65°C, the reaction time is 23-24 h. After the etherification reaction is completed, the temperature is lowered to 25°C, and the reaction product is purified by column chromatography, and the volume ratio of petroleum ether to dichloromethane in the eluent is 10:1 to obtain intermediate I.

[0013] As a further optimization of the above technical solution, in step S2, the temperature of the cyclization reaction is 25-35°C, the reaction time is 5-6 h. After the cyclization reaction is completed, the reaction product is purified by column chromatography, and the volume ratio of petroleum ether to dichloromethane in the column chromatography eluent is 1:1 to obtain intermediate II.

[0014] As a further optimization of the above technical solution, in step S3, the temperature of the substitution reaction is 70-80°C, the reaction time is 24-25 h. After the substitution reaction is completed, the temperature is lowered to 25°C, and the reaction product is purified by column chromatography, and the volume ratio of dichloromethane to methanol in the column chromatography eluent is 20:1 to obtain the ester-functionalized cyclotriveratrylene.

[0015] As a further optimization of the above technical solution, in step S1, the molar ratio of 1,2-dihydroxybenzene, 1,10-dibromodecane, and potassium carbonate is 1.0:4.0 - 4.1:3.0 - 3.1; in step S2, the molar ratio of intermediate I, paraformaldehyde, and sulfuric acid is 1.0:1.0 - 1.1:2.0 - 2.1; in step S3, the molar ratio of intermediate II and potassium acetate is 1.0:17.0 - 17.1.

[0016] In the third aspect of the present invention, a capillary gas chromatography column prepared by using the above ester-functionalized cyclotriveratrylene is proposed. The stationary phase of the capillary gas chromatography column is ester-functionalized cyclotriveratrylene.

[0017] As a further optimization of the above technical solution, the preparation method of the capillary gas chromatography column is the static coating method.

[0018] In the fourth aspect of the present invention, the application of the above capillary gas chromatography column in separating benzene series, homologues, dimethylnaphthalene isomers, diethylbenzene isomers, methylbenzaldehyde isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, cis-trans isomers, or multiple groups of complex mixtures is verified. The benzene series includes toluene, ethylbenzene, isopropylbenzene, propylbenzene, sec-butylbenzene, and butylbenzene. The homologues include bromododecane, bromoundecane, bromodecane, bromononane, bromooctane, bromoheptane, bromohexane, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-hexane, 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. The dimethylnaphthalene isomers include 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene, and 1,2-dimethylnaphthalene. The diethylbenzene isomers include 1,3-diethylbenzene, 1,4-diethylbenzene, and 1,2-diethylbenzene. The methylbenzaldehyde isomers include o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde. The bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde. The nitrobenzaldehyde isomers include o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde. The multiple groups of cis-trans isomers include cis-1,3-dichloropropene and trans-1,3-dichloropropene, cis-2-butenenitrile and trans-2-butenenitrile, cis-2-methyl-4-propyl-1,3-oxathiacyclohexane and trans-2-methyl-4-propyl-1,3-oxathiacyclohexane, cis-2-ethyl-2-hexenal and trans-2-ethyl-2-hexenal, cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-nerolidol and trans-nerolidol, cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate; The 22-component complex mixture is a mixture of amyl alcohol, 2-heptanone, propylbenzene, hexanol, o-chlorotoluene, bromoheptane, 1,2-diethylbenzene, methyl octanoate, pentylbenzene, tridecane, methyl nonanoate, nonanol, 2-undecanone, 2,4-dimethylaniline, pentadecane, 3,4-dimethylaniline, 2-methylnaphthalene, 2,5-dimethylphenol, o-chloronitrobenzene, 2,6-dimethylnaphthalene, p-bromonitrobenzene and 1,2-dimethylnaphthalene.

[0019] Meanwhile, the present invention also verifies the application of the above-mentioned capillary gas chromatography column in detecting the concentrations of 1,2,4-trichlorobenzene, o-xylene and trans-decalin.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The ester-functionalized cyclotriveratrylene prepared by the present invention can introduce a long alkyl chain to reduce the melting point of cyclotriveratrylene, improve the film-forming property and inertness of the stationary phase, and introduce an ester functional group to regulate the chromatographic separation performance of the stationary phase. Especially for some polar components, it can increase the hydrogen bond interaction and dipole-dipole interaction between the stationary phase and the analyte, so that the capillary gas chromatography column prepared with the ester-functionalized cyclotriveratrylene as the stationary phase has good separation performance for methylbenzaldehyde.

[0021] 2. The ester-functionalized cyclotriveratrylene prepared by the present invention combines the structural characteristics of cyclotriveratrylene and the advantages of ester functionalization. Cyclotriveratrylene is easy to be chemically modified, has high chemical stability, and has a unique C 3Due to advantages such as symmetric structure and electron-rich cavity, the present invention modifies cyclotriveratrylene by introducing long alkyl chains and ester groups along the lower edge of cyclotriveratrylene, improving the properties of cyclotriveratrylene as a gas chromatography stationary phase. Compared with cyclotriveratrylene before modification, the melting point of the ester-functionalized cyclotriveratrylene prepared by modification is decreased, the film-forming property and thermal stability are improved, and the separation performance of the stationary phase of cyclotriveratrylene used in capillary gas chromatography columns for analytes is also improved. The ester-functionalized cyclotriveratrylene can effectively separate benzene series, homologues, diethylbenzene isomers, methylbenzaldehyde isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, 8 groups of cis-trans isomers, and 22-component complex mixtures. Description of the Drawings

[0022] Figure 1 is the reaction diagram for preparing ester-functionalized cyclotriveratrylene from 1,2-dihydroxybenzene as the raw material in the present invention; Figure 2 is the column efficiency (Golay curve) diagram of the capillary gas chromatography column prepared in the present invention measured at 120 °C with n-dodecane as the analyte; Figure 3 is the chromatogram of the capillary gas chromatography column prepared in the present invention for separating benzene series and various homologues, where the benzene series includes toluene, ethylbenzene, isopropylbenzene, propylbenzene, sec-butylbenzene, and butylbenzene; various homologues include bromododecane, bromoundecane, bromodecane, bromononane, bromooctane, bromoheptane, bromohexane, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-hexane, 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; Figure 4 is the chromatogram of the capillary gas chromatography column prepared in the present invention for separating isomers substituted with different groups, and the isomers substituted with different groups include 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene, 1,2-dimethylnaphthalene, 1,3-diethylbenzene, 1,4-diethylbenzene, 1,2-diethylbenzene, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde; Figure 5 is the chromatogram of the capillary gas chromatography column prepared in the present invention for separating diethylbenzene isomers and comparing with the commercial columns HP-5 and HP-35, and the diethylbenzene isomers include 1,3-diethylbenzene, 1,4-diethylbenzene, and 1,2-diethylbenzene; Figure 6It is the chromatogram of separating benzaldehyde isomers substituted with different groups by the capillary gas chromatography column prepared in the present invention and compared with the commercial columns HP-5 and HP-35. Among them, the benzaldehyde isomers substituted with different groups include bromobenzaldehyde isomers and nitrobenzaldehyde isomers. The bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde; the nitrobenzaldehyde isomers include o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde; Figure 7 It is the chromatogram of separating 8 groups of cis-trans isomers with different polarities by the capillary gas chromatography column prepared in the present invention. Among them, (a): cis-1,3-dichloropropene, trans-1,3-dichloropropene, (b): cis-2-butenenitrile, trans-2-butenenitrile, (c): cis-2-methyl-4-propyl-1,3-oxathiolane, trans-2-methyl-4-propyl-1,3-oxathiolane, (d): cis-2-ethyl-2-hexenal, trans-2-ethyl-2-hexenal, (e): cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran, trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran, (f): cis-4-tert-butylcyclohexanol, trans-4-tert-butylcyclohexanol, (g): cis-nerolidol, trans-nerolidol, (h): cis-methyl dihydrojasmonate, trans-methyl dihydrojasmonate; Figure 8 It is the chromatogram of separating a 22-component complex mixture sample with different polarities and different types by the capillary gas chromatography column prepared in the present invention; in the figure, 1: pentanol, 2: 2-heptanone, 3: propylbenzene, 4: hexanol, 5: o-chlorotoluene, 6: bromoheptane, 7: 1,2-diethylbenzene, 8: methyl octanoate, 9: pentylbenzene, 10: tridecane, 11: methyl nonanoate, 12: nonanol, 13: 2-undecanone, 14: 2,4-dimethylaniline, 15: pentadecane, 16: 3,4-dimethylaniline, 17: 2-methylnaphthalene, 18: 2,5-dimethylphenol, 19: o-chloronitrobenzene, 20: 2,6-dimethylnaphthalene, 21: p-bromonitrobenzene, 22: 1,2-dimethylnaphthalene; Figure 9 It is the chromatogram of separating methylbenzaldehyde isomers by the capillary gas chromatography column prepared in 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 ester-functionalized pillar[6]arene as the stationary phase; in the figure, CTV-C10-0Ac is the capillary gas chromatography column prepared in the present invention, CTV is the capillary gas chromatography column prepared with ordinary cyclotriveratrylene as the stationary phase, and P6A-C10-20AC is the capillary gas chromatography column prepared with ester-functionalized pillar[6]arene as the stationary phase; Figure 10It is the chromatogram of three actual samples detected by the capillary gas chromatography column prepared by the present invention. The three actual samples include: 1,2,4-trichlorobenzene actual sample, o-xylene actual sample and trans-decahydronaphthalene actual sample; Figure 11 It is the thermogravimetric diagram of ester-functionalized cyclotriveratrylene. Specific embodiments

[0023] The technical solution of the present invention will be further elaborated in detail below in conjunction with specific embodiments. For 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 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.

[0024] The present invention discloses an ester-functionalized cyclotriveratrylene and its preparation method. As Figure 1 shown, the present invention uses 1,2-dihydroxybenzene as a raw material. First, intermediate I is obtained through an etherification reaction. Secondly, intermediate I undergoes a cyclization reaction to obtain intermediate II. Finally, intermediate II undergoes a substitution reaction to obtain an ester-functionalized cyclotriveratrylene. The chemical formula of this ester-functionalized cyclotriveratrylene is named CTV-C10-OAc, and the chemical structural formula of this ester-functionalized cyclotriveratrylene is: .

[0025] During the entire preparation process of the ester-functionalized cyclotriveratrylene, the reaction conditions are mild, the cost is low, and the steps are few. The structure of this ester-functionalized cyclotriveratrylene is novel, and the stability shown is good. When it is used as the stationary phase of a capillary gas chromatography column, it has a good separation effect on the analytes.

[0026] The ester-functionalized cyclotriveratrylene prepared by the present invention combines the structural characteristics of cyclotriveratrylene and the advantages of ester-functionalization. Among them, cyclotriveratrylene has the advantages of being easy to chemically modify, high chemical stability, having a unique C 3 symmetric structure and an electron-rich cavity, etc. Moreover, cyclotriveratrylene is easy to derivatize, and introducing non-polar long alkyl chains and polar ester groups can improve the properties of cyclotriveratrylene as a gas chromatography stationary phase, which can reduce the melting point of cyclotriveratrylene, improve the film-forming property, thermal stability of cyclotriveratrylene, and the separation performance of cyclotriveratrylene as the stationary phase of a capillary chromatographic column for analytes.

[0027] The present invention first roughens the inner surface of the capillary column by the traditional sodium chloride microcrystal deposition method for chromatographic column pretreatment. Secondly, the column is prepared by the static coating method, so that the stationary liquid prepared from CTV-C10-OAc is uniformly dispersed on the inner wall of the capillary column. Finally, the coated capillary chromatographic column is aged by a programmed temperature rise method under nitrogen protection, that is, the preparation of the capillary chromatographic column with CTV-C10-OAc as the stationary phase is completed. The stationary phase on the prepared capillary chromatographic column is uniformly coated on the inner wall of the capillary column.

[0028] The present invention first uses CTV-C10-OAc as the stationary phase of the capillary gas chromatographic column. CTV-C10-OAc combines the structural characteristics of cyclotriveratrylene and the advantages of ester group functionalization, making it a reality for CTV-C10-OAc to be used as the stationary phase of the capillary gas chromatographic column, and providing richer separation materials for the research of chromatographic separation.

[0029] Example 1 A preparation method of an ester group-functionalized cyclotriveratrylene, comprising the following steps: S1. Etherification reaction: React 1.00 g (9.08 mmol) of 1,2-dihydroxybenzene, 10.91 g (36.36 mmol) of 1,10-dibromodecane, 3.77 g (27.27 mmol) of potassium carbonate and 35 mL of N,N-dimethylformamide at 60 °C for 23 h. Let it stand and cool to 25 °C, distill off the solvent under reduced pressure, wash with deionized water, extract with petroleum ether, take the organic phase and dry it with anhydrous magnesium sulfate, distill off the solvent to obtain 6.12 g of crude product, and carry out column chromatography purification. The eluent is petroleum ether:dichloromethane = 10:1 (V:V) to obtain Intermediate I: 2.62 g. Intermediate I is a transparent oil, and the chemical structural formula of Intermediate I is as follows: ; The characterization data of Intermediate I are: 1 H NMR (400 MHz, CDCl 3 ) δ 6.89 (s, 4H), 3.99(t, J = 6.6 Hz, 4H), 3.41 (t, J = 6.8 Hz, 4H), 1.93 -1.77 (m, 8H), 1.5-1.4(m, 8H), 1.37-1.3 (m, 16H).IR (KBr,cm -1 ) : 644.08 (C-Br), 1042.87 (C-O-C),1022.74 (C-O-C),1466.62 (C=C),1453.01 ( C=C),2923.02 (CH 2 ).

[0030] S2, Cyclization Reaction: Add 1.00 g (1.82 mmol) of Intermediate Ⅰ, 0.05 g (1.67 mmol) of paraformaldehyde, and 15 mL of glacial acetic acid obtained in Step S1 into a 50 mL single-necked flask, react at 0 °C for 20 min, add 0.36 g (3.67 mmol) of sulfuric acid, react at 35 °C for 5 h, add an aqueous sodium hydroxide solution to quench the reaction, wash with saturated sodium chloride solution, filter by suction, take the filter cake and dry it to obtain 1.04 g of crude product. Perform column chromatography purification with the eluent of petroleum ether:dichloromethane = 1:1 (V:V) to obtain 0.23 g of Intermediate Ⅱ; Intermediate Ⅱ is a yellow oil, and the chemical structural formula of Intermediate Ⅱ is as follows: ; The characterization data of Intermediate Ⅱ are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ: 6.82 (s, 2H), 3.98 - 3.88 (m, 4H), 3.40 (t, J = 6.8 Hz, 4H), 1.86 - 1.74 (m, 8H), 1.45 - 1.29 (m, 24H). IR (KBr, cm -1 ):643.58 (C-Br), 1019.54 (C-O-C), 1259.24 (C-O-C), 1466.92 (C=C), 1508.85 (C=C), 2851.80 (CH 2 ), 2922.01 (CH 2 ).

[0031] S3, Substitution Reaction: Add 0.23 g (0.14 mmol) of Intermediate Ⅱ, 0.23 g (2.34 mmol) of potassium acetate, and 7 mL of N,N-dimethylformamide obtained in Step S2, react at 70 °C for 24 h, let it stand and cool down to 25 °C, add deionized water to quench, let it stand, solid precipitate appears, filter by suction, dry the filter cake to obtain 0.28 g of yellow crude product. Perform column chromatography purification with the eluent of dichloromethane:methanol = 20:1 (V:V) to obtain 0.14 g of ester-functionalized cyclotriveratrylene; this ester-functionalized cyclotriveratrylene is a yellow oil, and its chemical formula is CTV-C10-OAc, and the chemical structural formula is as follows: ; The characterization data of CTV-C10-OAc are as follows: 1 H NMR (400 MHz, CDCl 3) δ: 6.82 (s, 6H), 4.71 (d, J = 7.5 Hz, 3H), 4.04 (t, J = 6.8 Hz, 12H), 3.98 - 3.88 (m, 12H), 3.49 (d, J = 7.5 Hz, 3H), 2.04 (s, 18H), 1.81 - 1.59 (m, 24H), 1.44 - 1.29 (m, 74H). IR (KBr, cm -1 ):1036.20 (C - O - C), 1234.08 (C - O - C), 1468.98 (C = C), 1509.36 (C = C), 1735.70 (C = O), 2853.15 (CH 2 ) , 2923.36 (CH 2 ).

[0032] Example 2 In this example, the chemical structural formulas of Intermediate Ⅰ, Intermediate Ⅱ and CTV - C10 - OAc are the same as those in Example 1. The difference lies in the following different reaction conditions: S1. Etherification reaction: 1.50 g (13.62 mmol) of 1,2 - dihydroxybenzene, 16.56 g (55.17 mmol) of 1,10 - dibromodecane, 5.74 g (41.55 mmol) of potassium carbonate and 40 mL of N,N - dimethylformamide were reacted at 63 °C for 23.5 h. After standing and cooling to 25 °C, the solvent was evaporated under reduced pressure until dry. Deionized water was added, and extraction was carried out with petroleum ether. The organic phase was dried with anhydrous magnesium sulfate and then evaporated to dryness to obtain 10.65 g of crude product. Column chromatography purification was carried out, and the eluent was petroleum ether: dichloromethane = 10:1 (V:V), obtaining 3.11 g of Intermediate Ⅰ. Intermediate Ⅰ is a transparent oil.

[0033] S2. Cyclization reaction: 1.60 g (2.92 mmol) of Intermediate Ⅰ obtained in step S1, 0.09 g (2.30 mmol) of paraformaldehyde and 16 mL of glacial acetic acid were added to a 50 mL single - neck flask and reacted at 0 °C for 20 min. Then 0.58 g (5.91 mmol) of sulfuric acid was added, and the reaction was carried out at 30 °C for 5.5 h. The reaction was quenched with an aqueous sodium hydroxide solution, washed with saturated sodium chloride solution, filtered by suction and evaporated to dryness to obtain 1.63 g of crude product. Column chromatography purification was carried out, and the eluent was petroleum ether: dichloromethane = 1:1 (V:V), obtaining 0.34 g of Intermediate Ⅱ. Intermediate Ⅱ is a yellow oil.

[0034] S3. Substitution reaction: React 0.34 g (0.20 mmol) of intermediate II obtained in step S2, 0.34 g (3.46 mmol) of potassium acetate, and 10 mL of N,N-dimethylformamide at 75 °C for 24.5 h. Let it stand and cool to 25 °C. After quenching with deionized water, let it stand. A solid precipitates. Filter by suction. After drying the filter cake, 0.36 g of a yellow crude product is obtained. Purify it by column chromatography. The eluent is dichloromethane:methanol = 20:1 (V:V) to obtain 0.31 g of ester-functionalized cyclotriveratrylene. This ester-functionalized cyclotriveratrylene is a yellow oil with the chemical formula CTV-C10-OAc.

[0035] Example 3 In this example, the chemical structural formulas of intermediate I, intermediate II, and CTV-C10-OAc are the same as those in Example 1, except that the following reaction conditions are different: S1. Etherification reaction: React 2.00 g (18.16 mmol) of 1,2-dihydroxybenzene, 22.29 g (74.28 mmol) of 1,10-dibromodecane, 7.755 g (56.11 mmol) of potassium carbonate, and 45 mL of N,N-dimethylformamide at 65 °C for 24 h. Let it stand and cool to 25 °C. Distill off the solvent under reduced pressure until it is completely dry. Quench with deionized water and extract with petroleum ether. Take the organic phase and dry it with anhydrous magnesium sulfate. Evaporate to dryness to obtain 15.22 g of a crude product. Purify it by column chromatography. The eluent is petroleum ether:dichloromethane = 10:1 (V:V) to obtain 5.41 g of intermediate I. Intermediate I is a transparent oil.

[0036] S2. Cyclization reaction: Add 2.30 g (4.19 mmol) of intermediate I obtained in step S1, 0.13 g (4.33 mmol) of paraformaldehyde, and 19 mL of glacial acetic acid to a 50 mL single-necked flask. React at 0 °C for 20 min. Add 0.83 g (8.46 mmol) of sulfuric acid and react at 25 °C for 6 h. Quench the reaction with an aqueous sodium hydroxide solution, wash with saturated sodium chloride solution, filter by suction, and evaporate to dryness to obtain 1.97 g of a crude product. Purify it by column chromatography. The eluent is petroleum ether:dichloromethane = 5:1 (V:V) to obtain 0.46 g of intermediate II. Intermediate II is a yellow oil.

[0037] S3. Substitution reaction: React 0.46 g (0.27 mmol) of Intermediate II obtained in Step S2, 0.45 g (4.59 mmol) of potassium acetate, and 7 mL of N,N-dimethylformamide at 80 °C for 25 h. Let it stand and cool to 25 °C. After quenching with deionized water, let it stand, and a solid will precipitate. Perform suction filtration. After drying the filter cake, 0.48 g of a yellow crude product is obtained. Purify it by column chromatography with the eluent being dichloromethane:methanol = 20:1 (V:V) to obtain 0.44 g of ester-functionalized cyclotriveratrylene. This ester-functionalized cyclotriveratrylene is a yellow oil, and its chemical formula is CTV-C10-OAc.

[0038] Example 4 This example provides a capillary gas chromatography column. This capillary gas chromatography column uses the ester-functionalized cyclotriveratrylene prepared in Example 1 as the stationary phase material. The specific preparation method of the capillary gas chromatography column is as follows: (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.

[0039] (2) Weigh 1.31 g of ground NaCl powder, place it in 10 mL of anhydrous methanol solution, and 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 with vigorous stirring, then add 0.6 mL of anhydrous methanol solution, stir for 5 min, and then add 8 mL of dichloromethane solution and continue stirring for 2 min to obtain a saturated colloidal solution. Complete the roughening of the inner surface of the capillary column.

[0040] (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. Recrystallize it at 200 °C for 3 h under nitrogen protection.

[0041] (4) In this experiment, the column is prepared by the static coating method. Dissolve the CTV-C10-OAc prepared in Example 1 in dichloromethane solution to prepare a stationary liquid with a concentration of 0.15% (w / v), and ultrasonically treat it for 5 min to remove the bubbles in the stationary liquid.

[0042] (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.

[0043] (6) The capillary chromatographic column coated as above is aged by a programmed temperature method under nitrogen protection: maintained at 40 °C for 30 min, then raised to 180 °C at a rate of 1 °C / min and maintained for 7 h, thus completing the aging of the chromatographic column and obtaining the capillary gas chromatographic column.

[0044] In order to detect the performance of the ester-functionalized cyclotriveratrylene and the separation effect of the capillary chromatographic column, the following experiments are carried out on the capillary chromatographic column prepared in Example 4 of the present invention: <Determination of n-dodecane> As Figure 2 shown, the Golay curve of n-dodecane is measured using the capillary gas chromatographic 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.

[0045] From Figure 2 it can be seen that the capillary gas chromatographic column prepared by the static coating method using CTV-C10-OAc selected in the present invention as the chromatographic separation stationary phase has a high column efficiency.

[0046] <Separation of benzene series and various homologues> Different benzene series are selected as analytes, including toluene, ethylbenzene, isopropylbenzene, n-propylbenzene, sec-butylbenzene, and n-butylbenzene; Various homologues are selected as analytes, including 1-bromododecane, 1-bromoundecane, 1-bromodecane, 1-bromononane, 1-bromooctane, 1-bromoheptane, 1-bromohexane, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-hexane, 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.

[0047] Chromatographic separation conditions: maintained at 40 °C for 1 min, raised to 160 °C at a heating rate of 10 °C / min, and carrier gas flow rate 0.6 mL / min.

[0048] Figure 3 is the chromatogram of the separation of benzene series and various homologues by the capillary gas chromatographic column. From Figure 3 it can be known that the capillary gas chromatographic column prepared in the present invention can separate each component in the above-mentioned benzene series and homologues.

[0049] From Figure 3It can also be seen that the symmetry factor ranges of the mixed alcohols (i.e., pentanol, hexanol, heptanol, octanol, nonanol, and decanol) and mixed aldehydes (i.e., pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, and dodecanal) in the homologues are in the range of 0.95 - 1.05, and the chromatographic peak shapes are symmetrical and sharp, proving that the stationary phase CTV-C10-OAc is evenly coated on the inner wall of the capillary gas chromatography column and has good film-forming properties.

[0050] Combined with Figure 11 to further analyze the performance of CTV-C10-OAc, Figure 11 Figure Figure 11 is the thermogravimetric diagram of CTV-C10-OAc. It can be seen that at 289 °C, the weight loss is 5%, indicating that CTV-C10-OAc has good thermal stability.

[0051] At the same time, as is well known, the melting point of unmodified ordinary cyclotriveratrylene is 230 °C, while the ester-functionalized cyclotriveratrylene prepared in the present invention is a yellow oil at room temperature. It can be seen that the melting point of the ester-functionalized cyclotriveratrylene is lower than that of ordinary cyclotriveratrylene.

[0052] <Separation of positional isomers substituted with different groups> Select positional isomers substituted with different groups as analytes. The positional isomers substituted with different groups include dimethylnaphthalene isomers, diethylbenzene isomers, bromobenzaldehyde isomers, and nitrobenzaldehyde isomers. Among them, the dimethylnaphthalene isomers include 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene, and 1,2-dimethylnaphthalene; the diethylbenzene isomers include 1,3-diethylbenzene, 1,4-diethylbenzene, and 1,2-diethylbenzene; the bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde; the nitrobenzaldehyde isomers include o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde.

[0053] Chromatographic separation conditions: maintain at 40 °C for 1 min, and increase the temperature to 160 °C at a heating rate of 10 °C / min, with a carrier gas flow rate of 0.6 mL / min.

[0054] Figure 4 is the chromatogram of separating positional isomers substituted with different groups. It can be known from Figure 4 that the capillary gas chromatography column prepared in the present invention can separate the above-mentioned positional isomers substituted with different groups.

[0055] <Separation of diethylbenzene isomers> Select diethylbenzene isomers as analytes. The diethylbenzene isomers include 1,3-diethylbenzene, 1,4-diethylbenzene, and 1,2-diethylbenzene.

[0056] 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.

[0057] Figure 5 It is the chromatogram of separating diethylbenzene isomers with the capillary gas chromatographic column prepared in Example 4 and comparing with the commercial columns HP-5 and HP-35. As Figure 5 shown, the capillary gas chromatographic column prepared in Example 4 can effectively separate diethylbenzene isomers, and the effect is better than that of the polysiloxane commercial columns HP-5 and HP-35.

[0058] <Separation of benzaldehyde isomers substituted with different groups> Select benzaldehyde isomers substituted with different groups as the analytes. The benzaldehyde isomers substituted with different groups include bromobenzaldehyde isomers and nitrobenzaldehyde isomers. Among them, the bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde; the nitrobenzaldehyde isomers include o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde.

[0059] 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.

[0060] Figure 6 It is the chromatogram of separating benzaldehyde isomers substituted with different groups with the capillary gas chromatographic column prepared in Example 4 and comparing with the commercial columns HP-5 and HP-35. As Figure 6 shown, when separating benzaldehyde isomers substituted with different groups, the separation effect of the capillary gas chromatographic column prepared in Example 4 is better than that of the polysiloxane commercial columns HP-5 and HP-35.

[0061] <Separation of 8 groups of cis-trans isomers> Select 8 groups of cis-trans isomers as the analytes. The 8 groups of cis-trans isomers include: 1. cis-1,3-dichloropropene and trans-1,3-dichloropropene, 2. cis-2-butenenitrile and trans-2-butenenitrile, 3. cis-2-methyl-4-propyl-1,3-oxathiolane and trans-2-methyl-4-propyl-1,3-oxathiolane, 4. cis-2-ethyl-2-hexenal and trans-2-ethyl-2-hexenal, 5. cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran, 6. cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, 7. cis-nerylol and trans-nerylol, 8. cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate.

[0062] The capillary gas chromatography column prepared in Example 4 was used to separate the above 8-component cis-trans isomers. Chromatographic separation conditions: maintained at 40 °C for 1 min, heated to 160 °C at a heating rate of 10 °C / min, and carrier gas flow rate of 0.6 mL / min.

[0063] Figure 7 It is the chromatogram of the capillary gas chromatography column prepared in Example 4 for separating 8 groups of cis-trans isomers with different polarities. Among them, (a): cis-1,3-dichloropropene and trans-1,3-dichloropropene, (b): cis-2-butenenitrile and trans-2-butenenitrile, (c): cis-2-methyl-4-propyl-1,3-oxathiine and trans-2-methyl-4-propyl-1,3-oxathiine, (d): cis-2-ethyl-2-hexenal and trans-2-ethyl-2-hexenal, (e): cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran, (f): cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, (g): cis-nerolidol and trans-nerolidol, (h): cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate.

[0064] As Figure 7 shown, the capillary gas chromatography column prepared in Example 4 can completely separate each group of cis-trans isomers, demonstrating the advantage of CTV-C10-OA as a stationary phase for separating cis-trans isomers, with rapid and efficient separation.

[0065] <Separation of 22-component complex mixture> A 22-component complex mixture was selected as the analyte. The 22-component complex mixture is a mixture of pentanol, 2-heptanone, propylbenzene, hexanol, o-chlorotoluene, bromoheptane, 1,2-diethylbenzene, methyl octanoate, pentylbenzene, tridecane, methyl nonanoate, nonanol, 2-undecanone, 2,4-dimethylaniline, pentadecane, 3,4-dimethylaniline, 2-methylnaphthalene, 2,5-dimethylphenol, o-chloronitrobenzene, 2,6-dimethylnaphthalene, p-bromonitrobenzene, and 1,2-dimethylnaphthalene.

[0066] The capillary gas chromatography column prepared in Example 4 was used to separate the above 22-component complex mixture. Chromatographic separation conditions: maintained at 40 °C for 1 min, heated to 160 °C at a heating rate of 10 °C / min, and carrier gas flow rate of 0.6 mL / min.

[0067] Figure 8It is the chromatogram of the separation of a 22-component complex mixture by a capillary gas chromatography column. Among them, 1: pentanol, 2: 2-heptanone, 3: propylbenzene, 4: hexanol, 5: o-chlorotoluene, 6: bromoheptane, 7: 1,2-diethylbenzene, 8: methyl octanoate, 9: pentylbenzene, 10: tridecane, 11: methyl nonanoate, 12: nonanol, 13: 2-undecanone, 14: 2,4-dimethylaniline, 15: pentadecane, 16: 3,4-dimethylaniline, 17: 2-methylnaphthalene, 18: 2,5-dimethylphenol, 19: o-chloronitrobenzene, 20: 2,6-dimethylnaphthalene, 21: p-bromonitrobenzene, 22: 1,2-dimethylnaphthalene.

[0068] As Figure 8 shown, the capillary gas chromatography column prepared in Example 4 has a good separation effect on the 22-component complex mixture, with a relatively large number of analyte species and a wide polarity range. It demonstrates the good characteristics of CTV-C10-OAc as a stationary phase for separating complex mixtures.

[0069] <Separation of methylbenzaldehyde isomers> The capillary gas chromatography column prepared in Example 4, the capillary gas chromatography column prepared with ordinary cyclotriveratrylene, and the capillary gas chromatography column prepared with ester-functionalized pillar[6]arene were used to separate methylbenzaldehyde isomers. The methylbenzaldehyde isomers include o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde.

[0070] 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.

[0071] It can be Figure 9 seen that the capillary gas chromatography column prepared in Example 4 can separate methylbenzaldehyde isomers, but the capillary gas chromatography column prepared with ordinary cyclotriveratrylene as the stationary phase and the capillary gas chromatography column prepared with ester-functionalized pillar[6]arene as the stationary phase cannot separate the methylbenzaldehyde isomers. This is because the ester-functionalized cyclotriveratrylene has a unique C 3 symmetric structure and ester functional groups, and has a variety of different weak interactions with different analytes, so that the capillary gas chromatography column prepared with this ester-functionalized cyclotriveratrylene as the stationary phase can effectively separate methylbenzaldehyde isomers.

[0072] <Detection of three actual samples> Three actual samples were selected as analytes and detected with the capillary gas chromatography column prepared in Example 4. The three actual samples are 1,2,4-trichlorobenzene actual sample, o-xylene actual sample, and trans-decalin actual sample.

[0073] Chromatographic separation conditions: Maintain 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.

[0074] Figure 10 It is the chromatogram of 3 actual samples detected by a capillary gas chromatographic column. It can be seen that the capillary gas chromatographic column prepared in Example 4 detected the impurity isomers contained in the 3 actual samples.

[0075] As Figure 10 shown is the detection result of the impurity isomers in 3 actual samples by the capillary gas chromatographic column prepared in Example 4. Combining with Table 1, it can be known that the content is calculated by the method of peak area normalization, and the tested samples are all consistent with the purity on their labels.

[0076] Table 1 Physical sample Label purity (%) Test purity (%) Isomeric impurity Impurity content (%) 1,2,4-Trichlorobenzene 99.00 99.22 1,2,3-Trichlorobenzene 0.28 o-Xylene 99.00 98.91 m-Xylene / p-Xylene 0.72 trans-Decalin 99.00 99.45 cis-Decalin 0.17 As mentioned above, it 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 by 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. An ester-functionalized cyclotriveratrol, characterized in that: The chemical structural formula of the ester-functionalized cyclotriveratrol is: 。 2. A method for preparing the ester-functionalized cyclotriveratrol as claimed in claim 1, characterized in that: The following steps are involved: S1. Take 1,2-dihydroxybenzene, 1,10-dibromodecane, 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 obtained in step S1, paraformaldehyde, sulfuric acid and glacial acetic acid for cyclization reaction to obtain intermediate II. The chemical structure of intermediate II is: ； S3, taking the intermediate II obtained in step S2, potassium acetate and N,N-dimethylformamide for substitution reaction, and purifying the product after the substitution reaction is completed, so as to obtain the ester-functionalized cyclotriveratrol.

3. The method for preparing ester-functionalized cyclotriveratrol according to claim 2, characterized in that: The temperature of the etherification reaction in step S1 is 60-65° C., and the reaction time is 23-24 h. After the etherification reaction is completed, the temperature is lowered to 25° C., and the reaction product is purified by column chromatography, and the volume ratio of petroleum ether and dichloromethane in the column chromatography eluent is 10:1 to obtain intermediate I.

4. The method for preparing ester-functionalized cyclotriveratrol according to claim 2, characterized in that: In step S2, the temperature of the cyclization reaction is 25-35° C., and the reaction time is 5-6 h. After the cyclization reaction is completed, the reaction product is purified by column chromatography, and the volume ratio of petroleum ether and dichloromethane in the column chromatography eluent is 1:1 to obtain intermediate II.

5. The method for preparing ester-functionalized cyclotriveratrol according to claim 2, characterized in that: In step S3, the temperature of the substitution reaction is 70-80° C., and the reaction time is 24-25 h. After the substitution reaction is completed, the temperature is lowered to 25° C., and the reaction product is purified by column chromatography, and the volume ratio of dichloromethane and methanol in the column chromatography eluent is 20:1 to obtain ester-functionalized cyclotriveratrol.

6. The method for preparing ester-functionalized cyclotriveratrol according to claim 2, characterized in that: In step S1, the molar ratio of 1,2-dihydroxybenzene, 1,10-dibromodecane and potassium carbonate is 1.0:4.0-4.1:3.0-3.1; In step S2, the molar ratio of intermediate I, paraformaldehyde and sulfuric acid is 1.0:1.0~1.1:2.0~2.1; In step S3, the molar ratio of intermediate II to potassium acetate is 1.0:17.0-17.

1.

7. A capillary gas chromatography column, characterized in that: The stationary phase of the capillary gas chromatography column is the ester-functionalized cyclotriveratrol as claimed in claim 1.

8. A capillary gas chromatography column according to claim 7, characterized in that: The preparation method of the capillary gas chromatographic column is a static coating method.

9. Use of the capillary gas chromatography column as claimed in claim 7 in separating a mixture, characterized in that: The mixture is one of benzene series, homologous series, dimethylnaphthalene isomers, diethylbenzene isomers, methylbenzaldehyde isomers, bromobenzaldehyde isomers, nitrobenzaldehyde isomers, cis-trans isomers or a multi-component complex mixture; The benzene series include toluene, ethylbenzene, cumene, propylbenzene, sec-butylbenzene and butylbenzene; The homologues include brominated dodecane, brominated undecane, brominated decane, brominated nonane, brominated octane, brominated heptane, brominated hexane, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, valeraldehyde, hexanal, heptaldehyde, octanal, nonanal, decanal, undecanal, dodecanal, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, n-hexane, 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; The dimethylnaphthalene isomers include 2,6-dimethylnaphthalene, 1,3-dimethylnaphthalene, 2,3-dimethylnaphthalene and 1,2-dimethylnaphthalene; The diethylbenzene isomers include 1,3-diethylbenzene, 1,4-diethylbenzene and 1,2-diethylbenzene; The tolualdehyde isomers include o-tolualdehyde, m-tolualdehyde and p-tolualdehyde; The bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde; The nitrobenzaldehyde isomers include o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-nitrobenzaldehyde; The cis-trans isomers include a group consisting of cis-1,3-dichloropropylene and trans-1,3-dichloropropylene, cis-2-butenenitrile and trans-2-butenenitrile, cis-2-methyl-4-propyl-1,3-oxythiomercuric and trans-2-methyl-4-propyl-1,3-oxythiomercuric, cis-2-ethyl-2-hexenal and trans-2-ethyl-2-hexenal, cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydrofuran, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-nerolidol and trans-nerolidol, cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate; The multi-component complex mixture is a mixture of pentanol, 2-heptanone, propylbenzene, hexanol, o-chlorotoluene, heptane bromo, 1,2-diethylbenzene, methyl octanoate, pentylbenzene, tridecane, methyl nonanoate, nonanol, 2-undecanone, 2,4-xylidine, pentadecane, 3,4-xylidine, 2-methylnaphthalene, 2,5-dimethylphenol, o-chloronitrobenzene, 2,6-dimethylnaphthalene, p-bromonitrobenzene and 1,2-dimethylnaphthalene.

10. Use of the capillary gas chromatography column as claimed in claim 7 in detecting the concentrations of 1,2,4-trichlorobenzene, o-xylene and trans-decalin.

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