Alkyl-functionalized cyclotriveratrum hydrocarbon, preparation method thereof, capillary gas chromatographic column and application of capillary gas chromatographic column

Abstract

The invention discloses alkyl-functionalized cyclotriveratrum hydrocarbon and a preparation method thereof, a capillary gas chromatographic column and application, and relates to the technical field of gas chromatographic analys.The preparation method comprises the steps that 1, 2-hydroxybenzene serves as a raw material, an intermediate I is obtained through an etherification reaction, then the intermediate I is subjected to a cyclization reaction, the alkyl-functionalized cyclotriveratrum hydrocarbon is obtained, and the alkyl-functionalized cyclotriveratrum hydrocarbon is prepared. A long alkyl chain is introduced to the lower edge of cyclotriveratrum hydrocarbon, so that the property of the cyclotriveratrum hydrocarbon serving as a capillary gas chromatographic column stationary phase is improved, the melting point of the cyclotriveratrum hydrocarbon can be reduced by introducing the long alkyl chain, and the film-forming property and the thermal stability of the cyclotriveratrum hydrocarbon and the separation performance of the cyclotriveratrum hydrocarbon serving as a chromatographic stationary phase on an analyte are improved.

Description

Technical Field

[0001] The invention relates to the technical field of gas chromatography analysis, in particular to an alkyl-functionalized cyclotriveratrol and a preparation method thereof, a capillary gas chromatography column and 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 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 conjunction with infrared absorption spectroscopy or mass spectrometry, using chromatography 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 chromatographic column materials such as polysiloxanes and polyethylene glycols can achieve good separation of most substances. When faced with mixtures with very similar boiling points and polarities, or separation of positional isomers and cis-trans isomers, the materials that can be selected are very limited, so new capillary gas chromatography stationary phases with special selectivity and high stability are still being explored.

[0004] Macrocyclic compounds such as cyclotriveratrol, pillarhexaferrines, and pillarpentaferrines have become the main research objects of scientific researchers due to their inherent molecular recognition and complexing functions.

[0005] Reference 1: Paper “Separation Performance and Application of Cyclotriveratrol and Trimeric Indenes as New Gas Chromatographic Stationary Phases, Lv Qing, Beijing Institute of Technology, June 2016”.

[0006] Reference 1 discloses that the CTV (cyclotriveratrol) column has good separation effects on alkanes, esters, alkyl halides, halogenated benzenes, plasticizers, various positional isomers and cis-trans isomers. However, the film-forming property and thermal stability of cyclotriveratrol are relatively general. When it is used as the stationary phase of a capillary gas chromatography column, it is still unable to effectively separate chloronitrobenzene isomers, hydroquinone isomers, and phenylenediamine isomers.

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

[0008] Reference 2 discloses an alkyl-functionalized hexaaromatic column stationary phase, a capillary gas chromatography column, and a preparation method and application thereof. However, the alkyl-functionalized hexaaromatic column stationary phase still has a poor separation effect on chloronitrobenzene isomers, hydroquinone isomers, and phenylenediamine isomers. Summary of the invention

[0009] The present invention aims to provide an alkyl-functionalized cyclotriveratrol and a preparation method thereof, a capillary gas chromatography column and application thereof, so as to solve the problem of poor separation effect of macrocyclic compound p-chloronitrobenzene isomers, hydroquinone isomers and phenylenediamine isomers in the prior art.

[0010] In order to achieve the above object, the specific scheme adopted by the present invention is: an alkyl functionalized cyclotriveratrol, the chemical structure of the alkyl functionalized cyclotriveratrol is .

[0011] A method for preparing alkyl-functionalized cyclotriveratrol, comprising the following steps:

[0012] 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 ;

[0013] 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.

[0014] As a further optimization of the above technical solution, the temperature of the etherification reaction is 60-65°C, the reaction time is 23-24h, and after the reaction is completed, the temperature is lowered to 25°C, and the reaction product is purified by column chromatography using dichloromethane as an eluent 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 5-6h, the reaction product is purified by column chromatography, and the volume ratio of petroleum ether and 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, polyformaldehyde and sulfuric acid is 1.0:0.9~1.1:1.9~2.0.

[0018] A capillary gas chromatographic column, wherein the stationary phase of the capillary gas chromatographic column is alkyl-functionalized cyclotriveratrol.

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

[0020] A capillary gas chromatography column is used for 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, wherein the benzene series include toluene, ethylbenzene, isopropylbenzene, propylbenzene, sec-butylbenzene and butylbenzene;

[0021] 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;

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

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

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

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

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

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

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

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

[0030] The isomers of catechol include catechol, hydroquinone and resorcinol;

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

[0032] 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;

[0033] 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.

[0034] The invention discloses an 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 cyclotriveratrol prepared by the present invention has a unique C 3 The symmetrical structure and alkoxy chain functional groups have a variety of weak interactions with different analytes, including van der Waals forces, hydrogen bonds, π-π interactions, dipole-dipole interactions, etc., so that the capillary gas chromatography column prepared by using the alkyl-functionalized cyclotriveratrol as the stationary phase has good separation performance;

[0037] The alkyl-functionalized cyclotriveratrol prepared by the present invention combines the structural characteristics of cyclotriveratrol and the advantages of alkyl functionalization. By introducing a long alkyl chain at the lower edge of cyclotriveratrol, the properties of cyclotriveratrol as a capillary gas chromatography column stationary phase are improved. Compared with ordinary cyclotriveratrol, the alkyl-functionalized cyclotriveratrol prepared by the present invention has a lower melting point, improved film-forming properties and thermal stability, and also improved the separation performance of cyclotriveratrol used as a stationary phase for analytes, and can effectively separate 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a reaction diagram of the present invention for preparing alkyl-functionalized cyclotriveratrol using 1,2-dihydroxybenzene as a raw material;

[0039] Figure 2 is the thermogravimetric diagram of alkyl-functionalized cyclotriveratrol;

[0040] Figure 3 The column efficiency diagram of the capillary gas chromatographic column prepared by the present invention is measured at 120° C. using n-dodecane as the measured substance;

[0041] Figure 4 The present invention discloses a chromatogram of a capillary gas chromatography column for separating benzene series and various homologues, wherein the benzene series include toluene, ethylbenzene, isopropylbenzene, propylbenzene, sec-butylbenzene and butylbenzene; and various homologues 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;

[0042] Figure 5 The present invention discloses a chromatogram of positional isomers of different substituent groups separated by a capillary gas chromatography column, which includes: 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, and m-phenylenediamine.

[0043] Figure 6 The chromatograms are comparisons of the separation of benzaldehyde isomers with different group substitutions by the capillary gas chromatography column prepared in the present invention and the separation by commercial columns HP-5 and HP-35, including bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, and nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde;

[0044] Figure 7The chromatogram is a comparison of the separation of halogenated benzene isomers substituted with different groups by the capillary gas chromatography column prepared in the present invention and the separation by the commercial columns HP-5 and HP-35, 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;

[0045] Figure 8 The present invention discloses a chromatogram of 7 groups of cis-trans isomers of different polarities separated by a capillary gas chromatography column, wherein (a) is cis-1,3-dichloropropylene and trans-1,3-dichloropropylene, (b) is cis-2-butenenitrile and trans-2-butenenitrile, (c) is cis-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran and trans-4-methyl-2-(2-methyl-1-propenyl)tetrahydropyran, (d) is cis-4-tert-butyl cyclohexanol and trans-4-tert-butyl cyclohexanol, (e) is cis-nerolidol and trans-nerolidol, (f) is cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate, and (g) is cis-dimethyl citric acid acetal and trans-dimethyl citric acid acetal.

[0046] Fig. 9 The present invention discloses a chromatogram of a 22-component complex mixture sample of different polarities and types separated by a capillary gas chromatography column prepared by the present invention, wherein the 22-component complex mixture comprises 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, and 22: 3-iodoaniline.

[0047] Fig.10 The chromatogram is a comparison of the separation of chloronitrobenzene isomers by a capillary gas chromatography column prepared by the present invention, a capillary gas chromatography column prepared by using common cyclotriveratrol as the stationary phase, and a capillary gas chromatography column prepared by using alkyl-functionalized hexaaromatic hydrocarbon as the stationary phase; in the figure, CTV-C10 is a capillary gas chromatography column prepared by the present invention, CTV is a capillary gas chromatography column prepared by using common cyclotriveratrol as the stationary phase, and P6A-C10 is a capillary gas chromatography column prepared by using alkyl-functionalized hexaaromatic hydrocarbon as the stationary phase;

[0048] Fig.11The present invention discloses a chromatogram comparing the separation of hydroquinone isomers by a capillary gas chromatography column prepared by the present invention, a capillary gas chromatography column prepared by using common cyclotriveratrol as the stationary phase, and a capillary gas chromatography column prepared by using alkyl-functionalized hexaaromatic hydrocarbon as the stationary phase; in the figure, CTV-C10 is a capillary gas chromatography column prepared by the present invention, CTV is a capillary gas chromatography column prepared by using common cyclotriveratrol as the stationary phase, and P6A-C10 is a capillary gas chromatography column prepared by using alkyl-functionalized hexaaromatic hydrocarbon as the stationary phase;

[0049] Fig.12 The present invention discloses a chromatogram comparing the separation of phenylenediamine isomers by a capillary gas chromatography column prepared by the present invention, a capillary gas chromatography column prepared by using common cyclotriveratrol as the stationary phase, and a capillary gas chromatography column prepared by using alkyl-functionalized hexaaromatic hydrocarbon as the stationary phase; in the figure, CTV-C10 is a capillary gas chromatography column prepared by the present invention, CTV is a capillary gas chromatography column prepared by using common cyclotriveratrol as the stationary phase, and P6A-C10 is a capillary gas chromatography column prepared by using alkyl-functionalized hexaaromatic hydrocarbon as the stationary phase;

[0050] Fig.13 The invention discloses chromatograms of three actual samples detected by the capillary gas chromatography column prepared by the invention. The three actual samples include an actual sample of isopropylbenzene, an actual sample of cis-decalin and an actual sample of geraniol. DETAILED DESCRIPTION

[0051] The technical scheme of the present invention is further elaborated in detail below in conjunction with specific embodiments. The parts not described and disclosed in detail in the following embodiments of the present invention should 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 art; unless otherwise specified, the reagents and materials used in the present invention are commercially available.

[0052] like Figure 1 As shown, the present invention uses 1,2-dihydroxybenzene as a raw material, firstly obtains intermediate I through an etherification reaction, and then obtains alkyl-functionalized cyclotriveratrol through a cyclization reaction of intermediate I, which is named CTV-C10.

[0053] During the entire experimental operation process for preparing alkyl-functionalized cyclotriveratrol, the reaction conditions are mild, the cost is low, and the steps are few. The alkyl-functionalized cyclotriveratrol has a novel structure and exhibits good stability and has a good separation effect on the analytes.

[0054] The alkyl-functionalized cyclotriveratrol CTV-C10 prepared in the present invention combines the structural characteristics of cyclotriveratrol and the advantages of alkyl functionalization. Among them, cyclotriveratrol has the advantages of easy chemical modification, high chemical stability, and unique C 3 It has the advantages of symmetrical structure and electron-rich cavity, and cyclotriveratrol is easy to derivatize. The introduction of non-polar long alkyl chain improves the properties of cyclotriveratrol as a capillary gas chromatography column stationary phase, which can reduce the melting point of cyclotriveratrol, improve the film-forming property and thermal stability of cyclotriveratrol and the separation performance of cyclotriveratrol as a chromatographic stationary phase for analytes.

[0055] The invention firstly performs chromatographic column pretreatment by roughening the inner surface of a capillary column by a conventional sodium chloride microcrystal deposition method, then adopts a static coating method to prepare the column, so that a stationary liquid is evenly dispersed on the inner wall of the capillary column, and finally, the coated capillary chromatographic column is aged by a programmed temperature rising method under nitrogen protection, thus completing the preparation of the capillary chromatographic column, and the stationary phase on the prepared capillary chromatographic column is evenly 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, hydroquinone isomers, phenylenediamine isomers, 7 groups of cis-trans isomers, 22-component complex mixtures, etc.

[0057] The present invention uses CTV-C10 as the stationary phase of a capillary gas chromatographic column. CTV-C10 combines the structural characteristics of cyclotriveratrol and the advantages of alkyl functionalization, making it possible to use this new material as the stationary phase of a capillary gas chromatographic column, thereby providing more abundant separation materials for the research of chromatographic separation.

[0058] Example 1

[0059] A method for preparing alkyl-functionalized cyclotriveratrol, comprising the following steps:

[0060] S1. 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 were reacted at 60°C for 23 h, and the temperature was allowed to stand to cool to 25°C. The solvent was concentrated to dryness under reduced pressure, washed with deionized water, and filtered. The filter cake was dried to obtain a crude product. The crude product was dissolved in dichloromethane and filtered. The filtrate was evaporated to dryness to obtain intermediate I as a yellow-white solid: 2.89 g. The chemical structure of intermediate I is: .

[0061] The characterization data of intermediate Ⅰ are: mp40.1-40.7℃. 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, 6 H ) .IR (KBr ,cm -1 ): 1051.82 (COC), 1222.43 (COC), 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 obtained in step S1, 0.08 g (2.66 mmol) of polyformaldehyde and 15 mL of glacial acetic acid into 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 aqueous sodium hydroxide solution to quench the reaction, wash the organic phase with saturated sodium chloride solution, filter, evaporate to dryness, and obtain 1.12 g of crude product, which is purified by column chromatography with petroleum ether: dichloromethane = 5:1 (V:V) as the eluent to obtain 0.14 g of the final product Ⅱ as a yellow paste. The final product Ⅱ is CTV-C10.

[0063] The characterization data of the final product II are: 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(COC) ,1392.04(COC) ,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 embodiment and embodiment 1 is that the reaction conditions are different.

[0066] S1. React 1.50 g (13.62 mmol) 1,2-dihydroxybenzene, 8.80 g (39.79 mmol) 1-bromodecane, 7.45 g (53.91 mmol) potassium carbonate and 40 mL N,N-dimethylformamide at 63 °C for 23.5 h, let stand and cool to 25 °C, concentrate the solvent to dryness under reduced pressure, wash with deionized water and filter, dry the filter cake to obtain a crude product, dissolve the crude product in dichloromethane and filter, evaporate the filtrate to dryness to obtain a yellow-white solid intermediate I: 4.03 g.

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

[0068] Example 3

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

[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 stand and cool to 25 °C, concentrate the solvent to dryness under reduced pressure, wash with deionized water and filter, dry the filter cake to obtain a crude product, dissolve the crude product in dichloromethane and filter, evaporate the filtrate to dryness to obtain a yellow-white solid intermediate I: 6.01 g.

[0071] S2. Add 2 g (5.12 mmol) of intermediate Ⅰ obtained in step S1, 0.15 g (5.00 mmol) of polyformaldehyde 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, add aqueous sodium hydroxide solution to quench the reaction, wash the organic phase with saturated sodium chloride solution, filter, evaporate to dryness, and obtain 2.17 g of crude product, which is purified by column chromatography with an eluent of petroleum ether: dichloromethane = 5:1 (V:V) to obtain a yellow paste of final product Ⅱ: 0.45 g, which is CTV-C10.

[0072] Example 4

[0073] Preparation of capillary gas chromatographic 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 can flow out with the nitrogen at high temperature.

[0075] (2) Weigh 1.31 g of ground NaCl powder and place it in 10 mL of anhydrous methanol solution. Stir vigorously for 45 min to obtain a saturated sodium chloride methanol solution. Take 6 mL of the saturated solution and add it to 8 mL of dichloromethane solution that is being stirred vigorously. Then add 0.6 mL of anhydrous methanol solution and stir for 5 min. Then add 8 mL of dichloromethane solution and continue stirring for 2 min to obtain a saturated colloidal solution. The inner surface of the capillary column is roughened.

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

[0077] (4) In this experiment, a static column was prepared. The CTV-C10 prepared in Example 1 was dissolved in a dichloromethane solution to prepare a stationary phase with a concentration of 0.15% (w / v). The stationary phase was treated with ultrasound for 5 min to remove bubbles in the stationary phase.

[0078] (5) Use a syringe to push the stationary liquid into the capillary 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. The stationary liquid will then be evenly dispersed on the inner wall of the capillary column.

[0079] (6) Under nitrogen protection, the coated capillary column is aged by a programmed temperature rising method: starting from 40°C for 30 min, then increasing to 180°C at a rate of 1°C / min and maintaining for 7 h. This completes the aging of the column and obtains a capillary gas chromatography column.

[0080] 1. Thermogravimetric diagram of alkyl-functionalized cyclotriveratrol stationary phase

[0081] like Figure 2 The thermogravimetric diagram of alkyl-functionalized cyclotriveratrol is shown. In the present invention, CTV-C10 is used as the stationary phase of a 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 common cyclotriveratrol without any modification is 230 degrees Celsius, and it is a white solid at room temperature. The CTV-C10 prepared by the present invention is a paste at room temperature. It can be seen that the melting point of CTV-C10 is lower than that of common cyclotriveratrol.

[0083] 2. Example of separation effect of the capillary gas chromatography column prepared in Example 4

[0084] <Determination of n-dodecane>

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

[0086] It can be seen that the capillary gas chromatography column prepared by the static coating method of the present invention has a higher column efficiency.

[0087] <Separation of BTEX and various homologues>

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

[0089] Various homologues were selected as analytes, including dodecane bromide, undecane bromide, decane bromide, nonane bromide, octane bromide, heptane bromide, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, valeraldehyde, hexanal, heptaldehyde, 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, 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 a chromatogram of the capillary gas chromatographic column for separating benzene series and various homologues. It can be seen that the capillary gas chromatographic column prepared by the present invention can separate the above benzene series and various homologues.

[0092] like Figure 4 As shown, the symmetry factors of mixed alcohols and mixed aldehydes in the homologous series range from 0.95 to 1.05, and the chromatographic peaks 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 with different substitution groups>

[0094] Positional isomers substituted with different groups were selected 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, catechol, hydroquinone, resorcinol, 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 a chromatogram for separating positional isomers substituted with different groups. It can be seen that the capillary gas chromatographic column prepared by the present invention can separate positional isomers substituted with different groups.

[0097] <Separation of Benzaldehyde Isomers with Different Substitution Groups>

[0098] Benzaldehyde isomers substituted with different groups were selected as analytes, including bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, and p-bromobenzaldehyde, and nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, and 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 a chromatogram comparing the separation of benzaldehyde isomers with different group substitutions by capillary gas chromatography column with the separation of commercial columns HP-5 and HP-35, and the effect is better than that of commercial polysiloxane columns HP-5 and HP-35.

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

[0102] Halogenated benzene isomers substituted with different groups were selected as analytes, including dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, and chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene.

[0103] 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.

[0104] Figure 7 The chromatograms of the capillary gas chromatography column prepared in the example for separating halogenated benzene isomers substituted with different groups and the commercial columns HP-5 and HP-35 are shown in FIG. Figure 7 As shown, the capillary gas chromatography column prepared in the example can effectively separate halogenated benzene isomers substituted with different groups, and the effect is better than that of the commercial polysiloxane columns HP-5 and HP-35.

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

[0106] Seven components of cis-trans isomers were selected as analytes, including 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 capillary gas chromatography column prepared in the embodiment was used to separate the above 7 components of cis-trans isomers.

[0107] 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.

[0108] Figure 8The present invention is a chromatogram of 7 groups of cis-trans isomers of different polarities separated by a capillary gas chromatography column prepared in the embodiment, wherein: (a): cis-1,3-dichloropropylene and trans-1,3-dichloropropylene, (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-butyl cyclohexanol and trans-4-tert-butyl cyclohexanol, (e): cis-nerolidol and trans-nerolidol, (f): cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate, and (g): cis-citric acid dimethyl acetal and trans-citric acid dimethyl acetal.

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

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

[0111] A 22-component complex mixture is selected as an analyte, and 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. The capillary gas chromatography column prepared in the embodiment is used to separate the 22-component complex mixture.

[0112] 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.

[0113] Fig. 9 It is a chromatogram of a complex mixture of 22 components separated by a capillary gas chromatography column, among which: 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] like Fig. 9As shown, the capillary gas chromatography column prepared in the embodiment has a good separation effect on a complex mixture of 22 components, with a large variety of analytes and a wide polarity range, showing the good characteristics of CTV-C10 as a stationary phase suitable 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 using ordinary cyclotriveratrol and the capillary gas chromatography column P6A-C10 prepared using alkyl-functionalized hexaaromatic hydrocarbons are used to separate chloronitrobenzene isomers, and the chloronitrobenzene isomers include o-chloronitrobenzene, m-chloronitrobenzene and p-chloronitrobenzene.

[0117] 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.

[0118] Depend on Fig.10 It can be seen that the capillary gas chromatography column CTV-C10 prepared in Example 4 can separate chloronitrobenzene isomers, and the effect is better than the capillary gas chromatography column CTV prepared using ordinary cyclotriveratrol as the stationary phase and the capillary gas chromatography column P6A-C10 prepared using alkyl-functionalized hexaaromatic hydrocarbons.

[0119] <Separation of Hydroquinone Isomers>

[0120] The capillary gas chromatography column CTV-C10 prepared in Example 4, the capillary gas chromatography column CTV prepared using ordinary cyclotriveratrol, and the capillary gas chromatography column P6A-C10 prepared using alkyl-functionalized hexaaromatic hydrocarbons were used to separate catechol isomers, which include catechol, resorcinol and hydroquinone.

[0121] 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.

[0122] Depend on Fig.11 It can be seen that the capillary gas chromatography column CTV-C10 prepared in Example 4 can separate the isomers of diphenol, and the effect is better than the capillary gas chromatography column CTV prepared by using ordinary cyclotriveratrol as the stationary phase and the capillary gas chromatography column P6A-C10 prepared by using alkyl functionalized column hexaaromatic hydrocarbon. When the capillary gas chromatography column CTV prepared by using ordinary cyclotriveratrol as the stationary phase separates the isomers of diphenol, the analyte is not eluted, indicating that the capillary gas chromatography column CTV prepared by using ordinary cyclotriveratrol as the stationary phase cannot separate the isomers of diphenol.

[0123] <Separation of Phenylenediamine Isomers>

[0124] The capillary gas chromatography column CTV-C10 prepared in Example 4, the capillary gas chromatography column CTV prepared using ordinary cyclotriveratrol and the capillary gas chromatography column P6A-C10 prepared using alkyl-functionalized hexaaromatic hydrocarbons are 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] Depend on Fig.12 It can be seen that the capillary gas chromatography column CTV-C10 prepared in Example 4 can separate the isomers of phenylenediamine, and the effect is better than the capillary gas chromatography column CTV prepared by using ordinary cyclotriveratrol as the stationary phase and the capillary gas chromatography column P6A-C10 prepared by using alkyl-functionalized column hexaarene. Among them, when the capillary gas chromatography column P6A-C10 prepared by using alkyl-functionalized column hexaarene is used to separate the isomers of phenylenediamine, the analyte is not eluted. This is because the adsorption of alkyl-functionalized column hexaarene as the stationary phase to phenylenediamine isomers is too strong, resulting in the inability to separate the isomers of p-phenylenediamine.

[0127] 3. Testing three actual samples

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

[0129] Fig.13 The chromatograms of three actual samples detected by capillary gas chromatography columns include an actual sample of isopropylbenzene, an actual sample of cis-decalin, and an actual sample of geraniol. Fig.13 As shown, the capillary gas chromatography column prepared in the embodiment can detect isomeric impurities in three actual samples. As shown in Table 1, the actual sample content is calculated by peak area normalization method, and the actual samples tested are consistent with the purity on their labels.

[0130] Table 1 Actual samples Tag purity (%) Test purity (%) Isomer impurities 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 Nerolidol 0.67

[0131] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. An alkyl-functionalized cyclotriveratrol, characterized in that: The chemical structure of alkyl-functionalized cyclotriveratrol is .

2. The method for preparing an alkyl-functionalized cyclotriveratrol according to claim 1, characterized in that: The following steps are involved: 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. The method for preparing an alkyl-functionalized cyclotriveratrol according to 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. The method for preparing an alkyl-functionalized cyclotriveratrol according to 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. The method for preparing an alkyl-functionalized cyclotriveratrol according to 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. The method for preparing an alkyl-functionalized cyclotriveratrol according to 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. A capillary gas chromatography column, characterized in that: The stationary phase of the capillary gas chromatography column is the alkyl-functionalized cyclotriveratrol as claimed in claim 1.

8. A capillary gas chromatography column as claimed in 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 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.

10. Use of the capillary gas chromatography column as claimed in claim 7 in detecting the concentrations of isopropylbenzene, cis-decalin and geraniol.

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