CN117902959A - Alkyl functionalized hexa-arene used for stationary phase, preparation method thereof, capillary gas chromatographic column and application thereof - Google Patents
Alkyl functionalized hexa-arene used for stationary phase, preparation method thereof, capillary gas chromatographic column and application thereof Download PDFInfo
- Publication number
- CN117902959A CN117902959A CN202410059306.8A CN202410059306A CN117902959A CN 117902959 A CN117902959 A CN 117902959A CN 202410059306 A CN202410059306 A CN 202410059306A CN 117902959 A CN117902959 A CN 117902959A
- Authority
- CN
- China
- Prior art keywords
- cis
- trans
- hexa
- reaction
- arene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 36
- 230000005526 G1 to G0 transition Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 75
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960004337 hydroquinone Drugs 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims abstract description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 claims abstract description 3
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 claims description 22
- 238000003965 capillary gas chromatography Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims description 13
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000003935 benzaldehydes Chemical class 0.000 claims description 12
- SGVUHPSBDNVHKL-UHFFFAOYSA-N (+-)-trans-1,3-Dimethyl-cyclohexan Natural products CC1CCCC(C)C1 SGVUHPSBDNVHKL-UHFFFAOYSA-N 0.000 claims description 10
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 10
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims description 10
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 10
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 10
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 10
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 10
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 claims description 10
- CCOQPGVQAWPUPE-UHFFFAOYSA-N 4-tert-butylcyclohexan-1-ol Chemical compound CC(C)(C)C1CCC(O)CC1 CCOQPGVQAWPUPE-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 claims description 10
- XPQPWPZFBULGKT-UHFFFAOYSA-N methyl undecanoate Chemical compound CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 claims description 10
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 10
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 10
- 229960001860 salicylate Drugs 0.000 claims description 10
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 10
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 8
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 claims description 8
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims description 8
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 claims description 8
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims description 8
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 8
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 claims description 8
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000001555 benzenes Chemical class 0.000 claims description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 7
- 229940094933 n-dodecane Drugs 0.000 claims description 7
- 150000001448 anilines Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- SGVUHPSBDNVHKL-HTQZYQBOSA-N (1r,3r)-1,3-dimethylcyclohexane Chemical compound C[C@@H]1CCC[C@@H](C)C1 SGVUHPSBDNVHKL-HTQZYQBOSA-N 0.000 claims description 5
- SGVUHPSBDNVHKL-OCAPTIKFSA-N (1r,3s)-1,3-dimethylcyclohexane Chemical compound C[C@H]1CCC[C@@H](C)C1 SGVUHPSBDNVHKL-OCAPTIKFSA-N 0.000 claims description 5
- GFISDBXSWQMOND-PHDIDXHHSA-N (2r,5r)-2,5-dimethoxyoxolane Chemical compound CO[C@H]1CC[C@H](OC)O1 GFISDBXSWQMOND-PHDIDXHHSA-N 0.000 claims description 5
- GFISDBXSWQMOND-OLQVQODUSA-N (2r,5s)-2,5-dimethoxyoxolane Chemical compound CO[C@@H]1CC[C@H](OC)O1 GFISDBXSWQMOND-OLQVQODUSA-N 0.000 claims description 5
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 5
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 5
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 5
- FWIROFMBWVMWLB-UHFFFAOYSA-N 1-bromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1 FWIROFMBWVMWLB-UHFFFAOYSA-N 0.000 claims description 5
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims description 5
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 claims description 5
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 claims description 5
- HGZJJKZPPMFIBU-UHFFFAOYSA-N 3-formylbenzonitrile Chemical compound O=CC1=CC=CC(C#N)=C1 HGZJJKZPPMFIBU-UHFFFAOYSA-N 0.000 claims description 5
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 claims description 5
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 5
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 claims description 5
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 5
- 239000005641 Methyl octanoate Substances 0.000 claims description 5
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 claims description 5
- NNBZCPXTIHJBJL-AOOOYVTPSA-N cis-decalin Chemical compound C1CCC[C@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-AOOOYVTPSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 5
- NNBZCPXTIHJBJL-MGCOHNPYSA-N trans-decalin Chemical compound C1CCC[C@@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-MGCOHNPYSA-N 0.000 claims description 5
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical compound NC1=CC=CC=C1I UBPDKIDWEADHPP-UHFFFAOYSA-N 0.000 claims description 4
- FFCSRWGYGMRBGD-UHFFFAOYSA-N 3-iodoaniline Chemical compound NC1=CC=CC(I)=C1 FFCSRWGYGMRBGD-UHFFFAOYSA-N 0.000 claims description 4
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 claims description 4
- 229940078552 o-xylene Drugs 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 39
- 230000000694 effects Effects 0.000 abstract description 19
- -1 benzaldehyde isomer compounds Chemical class 0.000 abstract description 14
- 239000007789 gas Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 230000008901 benefit Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000013375 chromatographic separation Methods 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 8
- 150000005171 halobenzenes Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical class O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical class ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000007306 functionalization reaction Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical class INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FQTLCLSUCSAZDY-SDNWHVSQSA-N (6E)-nerolidol Chemical compound CC(C)=CCC\C(C)=C\CCC(C)(O)C=C FQTLCLSUCSAZDY-SDNWHVSQSA-N 0.000 description 3
- FQTLCLSUCSAZDY-KAMYIIQDSA-N (6Z)-nerolidol Chemical compound CC(C)=CCC\C(C)=C/CCC(C)(O)C=C FQTLCLSUCSAZDY-KAMYIIQDSA-N 0.000 description 3
- FQTLCLSUCSAZDY-SZGZABIGSA-N (E)-Nerolidol Natural products CC(C)=CCC\C(C)=C/CC[C@@](C)(O)C=C FQTLCLSUCSAZDY-SZGZABIGSA-N 0.000 description 3
- FQTLCLSUCSAZDY-ATGUSINASA-N (Z)-Nerolidol Natural products CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000004816 dichlorobenzenes Chemical class 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- ZLWGOLLBNDIBMM-UHFFFAOYSA-N trans-nerolidol Natural products CC(C)C(=C)C(O)CCC=C(/C)CCC=C(C)C ZLWGOLLBNDIBMM-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- WXFWXFIWDGJRSC-PHDIDXHHSA-N (2r,5r)-2,5-dimethoxy-2,5-dihydrofuran Chemical compound CO[C@@H]1O[C@@H](OC)C=C1 WXFWXFIWDGJRSC-PHDIDXHHSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JNYIQRMXGCWKOU-UHFFFAOYSA-M sodium methanol chloride Chemical class [Na+].[Cl-].OC JNYIQRMXGCWKOU-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of alkyl functionalized hexa-arene used for stationary phase, which comprises the following steps: step 1, etherifying monohalogenated hydrocarbon: heating 1, 4-benzenediol, 1-bromodecane, potassium hydroxide and ethanol for reaction, cooling, post-treating and purifying to obtain an intermediate (I); step 2, friedel-Crafts alkylation: reacting the intermediate (I), 1, 4-p-dichlorobenzyl, aluminum trichloride and methylene dichloride obtained in the step 1at room temperature, and after the reaction is finished, carrying out aftertreatment and purification to obtain an intermediate (II); step 3, ring closure: and (3) mixing the intermediate (II) obtained in the step (2), paraformaldehyde, boron trifluoride diethyl etherate and dichloromethane, and after the reaction is finished, performing post-treatment and purification to obtain alkyl functionalized hexa-aryl (III), wherein the alkyl functionalized hexa-aryl (III) has uniform particle size distribution on a capillary gas chromatographic column, and has better separation effect on substituted benzaldehyde isomer compounds and halogenated benzene isomer compounds.
Description
Technical Field
The invention belongs to the technical field of chromatographic analysis, and particularly relates to an alkyl functionalized hexa-arene used for a stationary phase, a preparation method thereof, a capillary gas chromatographic column and application thereof.
Background
Chromatography is the most commonly used analytical separation method in modern chemical industry systems. Gas chromatography is one of the most commonly used chromatographic separation techniques nowadays, and has been widely used for sample separation and analysis in various fields because of its advantages of high sensitivity, high selectivity, short analysis time, small sample consumption, and the like. The gas chromatography is one of the methods for qualitative and quantitative analysis of complex mixtures by separating each component in a sample by using the different physicochemical properties of the components, and further measuring the content of each component in the mixture. Compared with the traditional packed column, the capillary column has new improvement in separation efficiency and analysis speed.
In all structures of gas chromatography, the chromatographic column plays a main separation function, all separation processes of samples are completed in the chromatographic column, and the type of a stationary phase, a coating method, the thickness of a coating and the like of the sample can influence the column efficiency, the sensitivity of identification and the separation performance. The separation effect of the sample is mainly related to the nature of the stationary phase, so the stationary phase coated on the chromatographic column is critical to the separation process.
Some important supramolecular compounds, such as: crown ethers, cyclodextrins, calixarenes, cucurbiturils and column aromatics have been reported in the field of gas chromatography at present, but the fixation in the prior art is still poor compared with the separation of substituted benzaldehyde isomer compounds, aniline isomer compounds, halogenated benzene isomer compounds, partial cis-trans isomer compounds and complex mixtures, and the separation effect is not ideal. The oblique arene as a novel supermolecular compound has a unique cyclic molecular structure, and can have special chromatographic selectivity as a gas chromatographic stationary phase. In addition, the film forming property, the thermal stability, the chemical stability and the like of the diagonal aromatic hydrocarbon can be improved through alkylation modification.
Therefore, in order to solve the technical problems, the invention provides the alkyl functionalized hexa-arene used for the stationary phase, a preparation method thereof, a capillary gas chromatographic column and application thereof.
Disclosure of Invention
The invention aims to:
in order to overcome the shortcomings and drawbacks of the prior art, the present invention aims to: the invention provides an alkyl functionalized hexa-arene used for stationary phase, a preparation method thereof, a capillary gas chromatographic column and application thereof, and the capillary gas chromatographic column is prepared by a static coating method, and the application of the capillary gas chromatographic column is provided.
The technical scheme is as follows:
an alkyl functionalized hexa-arene for a stationary phase having the chemical structural formula:
a method for preparing alkyl functionalized hexa-arene used for stationary phase, which is carried out according to the following steps:
Step 1, etherifying monohalogenated hydrocarbon: heating 1, 4-benzenediol, 1-bromodecane, potassium hydroxide and ethanol for reaction, cooling, post-treating and purifying to obtain an intermediate (I);
Step 2, friedel-Crafts alkylation: reacting the intermediate (I), 1, 4-p-dichlorobenzyl, aluminum trichloride and methylene dichloride obtained in the step 1 at room temperature, finishing the reaction, performing post-treatment and purifying to obtain an intermediate (II);
Step 3, ring closure: mixing the intermediate (II) obtained in the step 2, paraformaldehyde, boron trifluoride diethyl etherate and dichloromethane, and after the reaction is finished, carrying out post-treatment and purification to obtain DeLP A (III), wherein the prepared DeLP A (III) has uniform particle size distribution on a capillary gas chromatographic column.
In the step 1, the temperature of the heating reaction is 80-85 ℃; the reaction time ranges from 4.5 to 5.5 hours; cooling to 25 ℃; the molar ratio of 1, 4-benzenediol to 1-bromodecane was 1.0:3.0 to 3.1; the molar ratio of 1, 4-benzenediol to potassium hydroxide is 1.0:3.0 to 3.1; the mass to volume ratio of the 1, 4-benzenediol, the 1-bromodecane, the potassium hydroxide and the ethanol is 1.0g:6.0 to 6.3g:1.5 to 1.6g: 22-25 mL; recrystallizing during purification, and using ethanol as solvent.
In step 2, the reaction is carried out at 25 ℃; the reaction time ranges from 2 to 3 hours; the molar ratio of 1, 4-p-dichlorobenzyl to intermediate (I) was 1.0:5.0 to 5.1; the molar ratio of 1, 4-p-dichlorobenzyl to potassium hydroxide is 1.0:3.0 to 3.1; the mass to volume ratio of 1, 4-p-dichlorobenzyl, intermediate (I), potassium hydroxide and methylene dichloride is 0.2g:2.2 to 2.3g:0.4 to 0.5g:25mL; recrystallizing during purification, and petroleum ether in solvent: the volume ratio of dichloromethane was 20:1.
In the step3, the reaction is carried out at 25-30 ℃; the reaction time ranges from 4 to 5 hours; the molar ratio of intermediate (II) to paraformaldehyde is 1.0:3.0 to 3.3; the molar ratio of intermediate (II) to boron trifluoride etherate was 1.0:1.2 to 1.3; the mass to volume ratio of the intermediate (II), paraformaldehyde, boron trifluoride diethyl etherate and methylene dichloride is 0.33g:0.03 to 0.04g:0.06 g-0.07 g:20mL; column chromatography was used for purification, and petroleum ether in eluent: the volume ratio of dichloromethane is 10:1.
A capillary gas chromatographic column is prepared from alkyl functionalized hexa-arene used for stationary phase by static method.
The application of the capillary gas chromatographic column can separate substituted benzaldehyde isomer, aniline isomer, halogenated benzene isomer, 8 groups of cis-trans isomers and 21 groups of complex mixtures; wherein,
Substituted benzaldehyde isomers include: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, o-cyanobenzaldehyde, m-cyanobenzaldehyde, p-cyanobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde;
the aniline isomers include: o-iodoaniline, m-iodoaniline, p-iodoaniline;
The halogenated benzene isomers include: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene;
Group 8 cis-trans isomers include: cis-3, 5-trimethylcyclohexane salicylate and trans-3, 5-trimethylcyclohexane salicylate, cis-1, 3-dimethylcyclohexane and trans-1, 3-dimethylcyclohexane, cis-nerol and trans-nerol, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-decalin and trans-decalin, cis-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dimethoxytetrahydrofuran, cis-2, 5-dihydro-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dihydro-2, 5-dimethoxytetrahydrofuran;
The 21-component complex mixture comprises: 2-hexanone, 1-bromopentane, o-xylene, o-chlorotoluene, 2-octanone, 1,2, 3-trimethylbenzene, m-dichlorobenzene, 1-octanol, methyl octanoate, o-toluidine, n-dodecane, 1,3, 5-trichlorobenzene, 2, 6-dimethylaniline, 2, 3-xylenol, n-tridecane, m-chloroaniline, m-chloronitrobenzene, 2-methylnaphthalene, methyl undecanoate, m-bromonitrobenzene, n-pentadecane.
The technical scheme of the invention has the advantages and effects that:
(1) According to the invention, 1, 4-benzenediol is used as a raw material, an intermediate (I) is obtained through etherification reaction, an intermediate (II) is obtained through Friedel-Crafts alkylation reaction, and the intermediate (II) is subjected to cyclization reaction to obtain alkyl functionalized hexa-arene (III) for stationary phase, which is named DeLP A, as shown in figure 1. The alkyl functionalized hexa-arene used for the stationary phase has the advantages of novel structure, obvious separation effect on analytes and good stability of the obtained final product, and the reaction condition is mild and the cost is low in the whole experimental operation process.
(2) The diagonal hexaarene DeLP A for alkyl functionalization of the stationary phase, which is prepared by the invention, combines the structural characteristics of the diagonal hexaarene and the advantages of alkyl functionalization. The oblique arene has the advantages of excellent host-guest property, structural flexibility and cavity adaptability and easy functionalization, so that the property of the oblique arene serving as a gas chromatographic stationary phase can be improved by introducing a long alkyl chain under the oblique arene, the melting point of the oblique arene can be reduced by introducing the long alkyl chain, the film forming property and the thermal stability of the oblique arene can be improved, and the separation performance of the oblique arene serving as a chromatographic stationary phase relative to a target compound can be improved.
(3) The alkyl functionalized hexa-arene DeLP A for stationary phase has unique cyclic structure and alkoxy chain functional group, so that the stationary phase has good effect in practical application and has various weak interaction forces with different analytes, and the method comprises the following steps: van der Waals forces, hydrogen bonding, pi-pi interactions, dipole-dipole interactions, and the like, result in DeLP A pillars with good separation properties.
(4) According to the invention, deLP A is used as a stationary phase of the capillary gas chromatographic column for the first time, deLP A perfectly combines the structural characteristics of oblique aromatic hydrocarbon and the advantages of alkyl functionalization, so that the novel material is used as the stationary phase of the capillary gas chromatographic column, and a richer separation material is provided for chromatographic separation research.
(5) The invention takes DeLP A as the stationary phase of the capillary gas chromatographic column for the first time, and has good thermal stability which is up to 308 ℃, as shown in figure 2.
(6) According to the invention, deLP A is used as a chromatographic separation stationary phase for the first time, and the capillary gas chromatographic column prepared by a static coating method has high column efficiency, as shown in figure 3.
(7) The capillary gas chromatographic column prepared by the invention has good separation performance on different analytes, and can separate substituted benzaldehyde isomers, wherein the substituted benzaldehyde isomers comprise methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, cyanobenzaldehyde isomers: o-cyanobenzaldehyde, m-cyanobenzaldehyde, p-cyanobenzaldehyde, nitrobenzaldehyde isomers: the separation effect of o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-nitrobenzaldehyde is superior to that of the polysiloxane commercial columns HP-5 and HP-35, as shown in figure 4.
Substituted aniline isomers, including the iodoaniline isomer: the separation effect of the o-iodoaniline, m-iodoaniline and p-iodoaniline is superior to that of the polysiloxane commercial columns HP-5 and HP-35, as shown in figure 5.
Substituted halobenzene isomers, including chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, chloronitrobenzene isomers: the separation effect of o-chloronitrobenzene, m-chloronitrobenzene and p-chloronitrobenzene is superior to that of polysiloxane commercial columns HP-5 and HP-35, as shown in figure 6.
Group 8 cis and trans isomers including cis-3, 5-trimethylcyclohexane salicylate and trans-3, 5-trimethylcyclohexane salicylate, cis-1, 3-dimethylcyclohexane and trans-1, 3-dimethylcyclohexane, cis-nerol and trans-nerol, cis-nerolidol and trans-nerolidol, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-decalin and trans-decalin, cis-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dimethoxytetrahydrofuran, cis-2, 5-dihydro-2, 5-dimethoxy tetrahydrofuran and trans-2, 5-dihydro-2, 5-dimethoxy tetrahydrofuran, as shown in FIG. 7.
A complex mixture of 21 components comprising: 2-hexanone, 1-bromopentane, o-xylene, o-chlorotoluene, 2-octanone, 1,2, 3-trimethylbenzene, m-dichlorobenzene, 1-octanol, methyl octanoate, o-toluidine, n-dodecane, 1,3, 5-trichlorobenzene, 2, 6-dimethylaniline, 2, 3-xylenol, n-tridecane, m-chloroaniline, m-chloronitrobenzene, 2-methylnaphthalene, methyl undecanoate, m-bromonitrobenzene and n-pentadecane, and the separation effect is better than that of polysiloxane commodity columns HP-5 and HP-35, as shown in figure 8.
(8) The capillary gas chromatographic column prepared by the invention has good separation performance on benzaldehyde isomers and halogenated benzene isomers, wherein the capillary gas chromatographic column comprises chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, methylbenzaldehyde isomers: the separation effect of the o-methylbenzaldehyde, m-methylbenzaldehyde and p-methylbenzaldehyde is superior to that of capillary gas chromatographic columns prepared from polysiloxane commercial columns HP-5 and HP-35 and alkyl functionalized column hexaaromatics, as shown in figure 9.
Drawings
The above, as well as additional purposes, features, and advantages of exemplary embodiments of the present invention will become readily apparent from the following detailed description when read in conjunction with the accompanying drawings. In the drawings, wherein like or corresponding reference numerals indicate like or corresponding parts, there are shown by way of illustration, and not limitation, several embodiments of the invention, in which:
FIG. 1 is a reaction scheme of an alkyl functionalized hexa-arene DeLP A prepared from 1, 4-benzenediol as a raw material according to the present invention.
FIG. 2 is a thermogravimetric plot of an alkyl functionalized diagonal aromatic stationary phase.
FIG. 3 is a graph showing the column effect (Golay curve) of a capillary gas chromatography column prepared by the present invention measured at 120℃using n-dodecane as a test substance.
FIG. 4 shows a comparison of the separation of different types of benzaldehyde isomers with different polarities by using a capillary gas chromatographic column prepared by the present invention, and the separation of commercial columns HP-5 and HP-35, wherein the separation comprises the methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, cyanobenzaldehyde isomers: o-cyanobenzaldehyde, m-cyanobenzaldehyde, p-cyanobenzaldehyde, nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde.
FIG. 5 is a capillary gas chromatography column separation of iodoaniline isomers from commercial columns HP-5 and HP-35 separation control made in accordance with the present invention: o-iodoaniline, m-iodoaniline, p-iodoaniline.
FIG. 6 is a comparison of the separation of different polarity different types of halobenzene isomers from commercial columns HP-5 and HP-35 by the capillary gas chromatography column prepared in accordance with the present invention, including the chlorotoluene isomer: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene.
FIG. 7 shows the separation of 8 sets of cis-trans isomers of different polarities by using the capillary gas chromatography column prepared in the present invention, wherein (a): cis-3, 5-trimethylcyclohexane salicylate, trans-3, 5-trimethylcyclohexane salicylate, (b): cis-1, 3-dimethylcyclohexane, trans-1, 3-dimethylcyclohexane, (c): cis-nerol, trans-nerol, (d): cis-nerolidol, trans-nerolidol, (e): cis-4-tert-butylcyclohexanol, trans-4-tert-butylcyclohexanol, (f): cis-decalin, trans-decalin, (g): cis-2, 5-dimethoxy tetrahydrofuran, trans-2, 5-dimethoxy tetrahydrofuran, (h): chromatograms of cis-2, 5-dihydro-2, 5-dimethoxyfuran, trans-2, 5-dihydro-2, 5-dimethoxyfuran.
FIG. 8 shows the separation of a complex mixture of 21 components of different polarities and different types from commercial columns HP-5 and HP-35 by a capillary gas chromatographic column prepared according to the present invention.
FIG. 9 is a capillary gas chromatography column separation of benzaldehyde and halobenzene isomers made in accordance with the present invention as compared to commercial columns HP-5, HP-35 and P6A-C10, including chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde.
Reference numerals illustrate:
1: 2-hexanone, 2: 1-bromopentane, 3: ortho-xylene, 4: o-chlorotoluene, 5: 2-octanone, 6:1,2, 3-trimethylbenzene, 7: m-dichlorobenzene, 8: 1-octanol, 9: methyl octanoate, 10: o-toluidine, 11: n-dodecane, 12:1,3, 5-trichlorobenzene, 13:2, 6-dimethylaniline, 14:2, 3-xylenol, 15: n-tridecane, 16: m-chloroaniline, 17: m-chloronitrobenzene, 18: 2-methylnaphthalene, 19: methyl undecanoate, 20: m-bromonitrobenzene, 21: n-pentadecane.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
The principle of the invention is as follows:
As shown in figure 1, the invention takes 1, 4-dihydroxybenzene as a raw material, firstly, an intermediate (I) is obtained through etherification reaction, secondly, the intermediate (I) is obtained through Friedel-Crafts alkylation reaction to obtain an intermediate (II), the intermediate (II) is subjected to cyclization reaction to obtain alkyl functionalized diagonal hexaarene DeLP A (III), and the prepared DeLP A has uniform particle size distribution on a chromatographic column.
The diagonal hexaarene DeLP A for alkyl functionalization of the stationary phase, which is prepared by the invention, combines the structural characteristics of the diagonal hexaarene and the advantages of alkyl functionalization. The oblique arene has the advantages of good structure flexibility, good host-guest properties, good cavity adaptability and the like, the oblique arene is easy to derivatize, the nonpolar long alkyl chain is introduced to improve the property of the oblique arene as a gas chromatographic stationary phase, the melting point of the oblique arene can be reduced, the film forming property and the thermal stability of the oblique arene can be improved, and the oblique arene can be used as a chromatographic fixed relative target compound to separate the performance.
Firstly, carrying out roughening chromatographic column pretreatment on the inner surface of a capillary column by a traditional sodium chloride microcrystalline deposition method, secondly, adopting a static coating method to prepare the column, uniformly dispersing a fixing liquid on the inner wall of the capillary column, and finally, aging the coated capillary chromatographic column under the protection of nitrogen by adopting a temperature programming method to prepare the DeLP A capillary chromatographic column.
The synthesis method of the alkyl functionalized hexa-arene DeLP A for stationary phase uses 1, 4-dihydroxybenzene as raw material, firstly, an intermediate (I) is obtained through etherification reaction, secondly, the intermediate (I) is obtained through Friedel-Crafts alkylation reaction to obtain an intermediate (II), and the intermediate (II) is subjected to cyclization reaction to obtain the alkyl functionalized hexa-arene derivative DeLP A (III).
Example 1:
1.00g (9.08 mmol) of 1, 4-benzenediol, 6.03g (27.24 mmol) of 1-bromodecane, 1.53g (27.24 mmol) of potassium hydroxide and 22mL of ethanol are reacted at 80 ℃ for 5.5h, deionized water is added to separate out solid, the solid is separated out after standing and cooling, suction filtration is carried out after filter cake drying to obtain crude product, recrystallization is carried out at 70 ℃, ethanol is taken as solvent, the solution is clarified and taken out for standing, the solid is separated out, suction filtration is carried out, and after filter cake drying, the intermediate (I) white solid is obtained ：2.60g.m.p.70.1-70.8℃.IR(KBr,cm-1):1028.65(C-O-C),1231.65(C-O-C),1409.22(C＝C),1463.21(C＝C),1473.74(C＝C),1509.98(C＝C),2849.81(CH2),2871.68(CH2),2955.00(CH3).
2.23G (5.17 mmol) of the intermediate (I) obtained in the step (1), 0.20g (1.14 mmol) of 1, 4-p-dichlorobenzyl chloride, 0.46g (3.43 mmol) of aluminum trichloride and 25mL of methylene chloride are added into a 50mL single-neck flask, reacted at 25 ℃ for 2.5h, deionized water is added, the solution is separated, the organic layer is dried with anhydrous magnesium sulfate, filtered and evaporated to dryness to obtain 2.21g of a pale yellow crude product, and column chromatography purification is carried out, wherein an eluent is petroleum ether: dichloromethane=20:1 (V: V) to afford intermediate (ii) as a white solid ：0.38g.1H NMR(400MHz,CDCl3)δ:7.00(s,4H),6.88(s,6H),4.15-3.44(m,12H),1.85-1.72(m,8H),1.65(q,J＝6.8Hz,4H),1.5-1.43(m,4H),1.40-1.27(m,48H),0.91(td,J＝6.8,3.2Hz,12H).IR(KBr,cm-1):1038.67(C-O-C),1239.75(C-O-C),1412.28(C＝C),1471.25(C＝C),1483.91(C＝C),2854.82(CH2),2868.17(CH2),2953.99(CH3).
Adding 0.32g (0.37 mmol) of the intermediate (II) obtained in the step (2), 0.3g (1.10 mmol) of paraformaldehyde and 20mL of methylene dichloride into a 50mL single-neck flask, reacting for 20min at 0 ℃, adding 0.06g (0.44 mmol) of boron trifluoride diethyl ether, reacting for 4h at 30 ℃, adding sodium hydroxide aqueous solution to quench the reaction, washing an organic phase with saturated sodium chloride solution, filtering by suction, evaporating to dryness to obtain 0.35g of crude product, and purifying by column chromatography, wherein an eluent is petroleum ether: dichloromethane=10:1 (V: V) to give a colorless oil DeLP6A(Ⅲ)：0.11g.1H NMR(300MHz,CDCl3)δ:6.97(s,8H),6.85(s,4H),6.56(s,4H),4.10-3.52(m,28H),1.76(m,8H),1.59(g,J＝6.7Hz,8H),1.43(d,J＝7.9Hz,8H),1.27(d,J＝7.4Hz,104H),0.88(td,J＝6.8,2.6Hz,24H).IR(KBr,cm-1):1046.77(C-O-C),1393.48(C-O-C),1409.22(C＝C),1467.59(C＝C),1504.16(C＝C),2850.86(CH2),2920.03(CH2).ESI-MS:m/z calculated for C122H196O8:1789.90(100％);found:1808.53[M+H2O+H]+(100％),1846.56[M+H2O+K]+(100％).
Example 2:
this experiment differs from example 1 in that: the reaction conditions are different.
1.50G (13.62 mmol) of 1, 4-benzenediol, 9.25g (41.86 mmol) of 1-bromodecane, 2.35g (41.94 mmol) of potassium hydroxide and 35mL of ethanol are reacted at 83 ℃ for 5.1h, deionized water is added to separate out solid, the solid is added, standing and cooling are carried out, suction filtration is carried out, a filter cake is dried to obtain a crude product, recrystallization is carried out at 70 ℃, ethanol is taken as solvent, the solution is clarified and taken out for standing, the solid is separated out, suction filtration is carried out, and after the filter cake is dried, the intermediate (I) white solid is obtained: 3.92g.
3.92G (10.24 mmol) of the intermediate (I) obtained in the step (1), 0.3g (1.71 mmol) of 1, 4-p-dichlorobenzyl chloride, 0.70g (5.21 mmol) of aluminum trichloride and 38mL of methylene chloride are added into a 100mL single-neck flask, reacted at 25 ℃ for 2.8h, deionized water is added, the solution is separated, the organic layer is dried with anhydrous magnesium sulfate, filtered and evaporated to dryness to obtain 3.48g of a light yellow crude product, and column chromatography purification is carried out, wherein the eluent is petroleum ether: dichloromethane=20:1 (V: V) to afford intermediate (ii) as a white solid: 0.55g.
Adding 0.49g (0.55 mmol) of the intermediate (II) obtained in the step (2), 0.05g (1.20 mmol) of paraformaldehyde and 30mL of methylene dichloride into a 50mL single-neck flask, reacting for 20min at 0 ℃, adding 0.10g (0.70 mmol) of boron trifluoride diethyl ether, reacting for 4.6h at 28 ℃, adding sodium hydroxide aqueous solution to quench the reaction, washing an organic phase with saturated sodium chloride solution, filtering by suction, evaporating to dryness to obtain 0.54g of crude product, and purifying by column chromatography, wherein an eluent is petroleum ether: dichloromethane=10:1 (V: V) to give DeLP a (iii) as a colourless oil: 0.11g.
Example 3:
this experiment differs from example 1 in that: the reaction conditions are different.
1.75G (15.89 mmol) of 1, 4-benzenediol, 10.89g (49.29 mmol) of 1-bromodecane, 2.77g (49.44 mmol) of potassium hydroxide and 44mL of ethanol are reacted at 85 ℃ for 4.5h, deionized water is added to separate out solid, the solid is added, standing and cooling are carried out, suction filtration is carried out, a filter cake is dried to obtain a crude product, recrystallization is carried out at 70 ℃, ethanol is taken as solvent, the solution is clarified and taken out for standing, the solid is separated out, suction filtration is carried out, and after the filter cake is dried, the intermediate (I) white solid is obtained: 4.71g.
4.64G (12.12 mmol) of the compound (I) obtained in the step (1), 0.35g (2.00 mmol) of 1, 4-p-dichlorobenzyl chloride, 0.83g (6.18 mmol) of aluminum trichloride and 44mL of methylene chloride are added into a 100mL single-neck flask, the mixture is reacted for 3 hours at 25 ℃, deionized water is added, the separated liquid is separated, the organic layer is dried by anhydrous magnesium sulfate, filtered and evaporated to dryness to obtain 3.98g of light yellow crude product, and column chromatography purification is carried out, wherein the eluent is petroleum ether: dichloromethane=20:1 (V: V) to afford intermediate (ii) as a white solid: 0.71g.
Adding 0.57g (0.65 mmol) of the intermediate (II) obtained in the step (2), 0.06g (2.12 mmol) of paraformaldehyde and 35mL of methylene dichloride into a 100mL single-neck flask, reacting for 20min at 0 ℃, adding 0.12g (0.83 mmol) of boron trifluoride diethyl ether, reacting for 5h at 25 ℃, adding sodium hydroxide aqueous solution to quench the reaction, washing an organic phase with saturated sodium chloride solution, filtering by suction, evaporating to dryness to obtain 0.71g of crude product, and purifying by column chromatography, wherein an eluent is petroleum ether: dichloromethane=10:1 (V: V) to give DeLP a (iii) as a colourless oil: 0.21g.
Example 4:
the preparation of the capillary gas chromatographic column comprises the following steps:
(1) A quartz capillary having a length of 5m and an inner diameter of 250 μm was cut out. Firstly, dichloromethane is used for flushing for 10min, then the capillary column is aged for 2-3h at 200 ℃ under the protection of nitrogen, so that impurities in the capillary column flow out along with the nitrogen at high temperature.
(2) 1.31G of the ground NaCl powder was weighed and placed in 10mL of an anhydrous methanol solution, and the mixture was stirred vigorously for 45 minutes to obtain a saturated sodium chloride methanol solution. 6mL of saturated solution is taken to be added into 8mL of dichloromethane solution which is strongly stirred, 0.6mL of absolute methanol solution is added, stirring is carried out for 5min, 8mL of dichloromethane solution is added, stirring is continued for 2min, and saturated colloidal solution is obtained. Roughening the inner surface of the capillary column is completed.
(3) The saturated colloidal solution was pressed into a capillary tube under an appropriate nitrogen pressure, and then the in-column solution was blown out with nitrogen, and recrystallized at 200 ℃ for 3 hours under nitrogen protection.
(4) The experiment adopts a static method to prepare a column, deLP A is dissolved in methylene dichloride solution to prepare a fixed liquid with the concentration of 0.15% (w/v), and ultrasonic treatment is carried out for 5min to remove bubbles in the fixed liquid.
(5) Pushing the fixing liquid into the capillary chromatographic column by using a syringe until the fixing liquid fills the whole chromatographic column, sealing one end of the capillary tube, connecting the other end of the capillary tube with a vacuum system, slowly evaporating the solvent in a constant-temperature water bath at 38 ℃, and uniformly dispersing the fixing liquid on the inner wall of the capillary column.
(6) Aging the coated capillary chromatographic column under the protection of nitrogen by adopting a temperature programming method: maintaining at 40deg.C for 30min, and then heating to 180deg.C at a rate of 1deg.C/min for 7 hr to obtain capillary gas chromatographic column.
Example 5:
separation effect of capillary gas chromatography column example:
(1) As shown in fig. 3, the Golay curve of n-dodecane was measured using the capillary gas chromatography column prepared in example 4, and the specific chromatographic conditions were: column box temperature 120 ℃, carrier gas: nitrogen, carrier gas flow rate: 17.14cm/s, the lowest theoretical plate height is: 0.21mm.
(2) The capillary gas chromatography column prepared in the examples separates the substituted benzaldehyde isomers
Different types of benzaldehyde isomers of different polarities are selected as the separated analytes, including the methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, cyanobenzaldehyde isomers: o-cyanobenzaldehyde, m-cyanobenzaldehyde, p-cyanobenzaldehyde, nitrobenzaldehyde isomers: o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
FIG. 4 shows the chromatograms of the capillary gas chromatographic column for separating different polarity different types of benzaldehyde isomers compared with commercial columns HP-5 and HP-35, and the effect is better than that of the commercial columns HP-5 and HP-35.
(3) The capillary gas chromatography column prepared in the example separates the iodoaniline isomer
FIG. 5 shows the separation of iodoaniline isomers by capillary gas chromatography columns prepared in the examples: the capillary gas chromatographic column prepared by the embodiment can effectively separate substituted aniline isomers and has better effect than polysiloxane commodity columns HP-5 and HP-35. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
(4) The capillary gas chromatography column prepared in the examples separates the substituted halobenzene isomers
Different types of halobenzene isomers of different polarities are selected as the separated analytes, including chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, dichlorobenzene isomers: o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
FIG. 6 is a chromatogram of the separation control of the halogenated benzene isomers from the commercial columns HP-5 and HP-35 by using the capillary gas chromatographic column prepared in the example, as shown in FIG. 6, the halogenated benzene isomers can be effectively separated by using the capillary gas chromatographic column prepared in the example, and the effect is better than that of the commercial columns HP-5 and HP-35 of polysiloxane.
(6) The capillary gas chromatographic column prepared in the example separates 8 groups of cis-trans isomers
The 8-component cis-trans isomer is selected as an analyte, and the isomer is separated by using the capillary gas chromatographic column prepared in the example. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
FIG. 7 is a chromatogram of a capillary gas chromatography column prepared in the example for separating 9 sets of cis-trans isomers of different polarities, wherein (a): cis-3, 5-trimethylcyclohexane salicylate and trans-3, 5-trimethylcyclohexane salicylate, (b): cis-1, 3-dimethylcyclohexane and trans-1, 3-dimethylcyclohexane, (c): cis-nerol and trans-nerol, (d): cis-nerolidol and trans-nerolidol, (e): cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, (f): cis-decalin and trans-decalin, (g): cis-2, 5-dimethoxy tetrahydrofuran and trans-2, 5-dimethoxy tetrahydrofuran, (h): cis-2, 5-dihydro-2, 5-dimethoxyfuran and trans-2, 5-dihydro-2, 5-dimethoxyfuran. As shown in FIG. 7, the capillary gas chromatographic column prepared by the embodiment can completely separate each group of cis-trans isomers, and has the advantage of DeLP A stationary phase for separating cis-trans isomers, and is rapid and efficient in separation.
(7) The capillary gas chromatography column prepared in the examples separates 21 component complex mixtures
A complex mixture of 21 components was selected as the analyte and the samples were separated using the capillary gas chromatography column prepared in the examples. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
Fig. 8 is a chromatogram of a capillary gas chromatography column separating a 21-component complex mixture, wherein 1: 2-hexanone, 2: 1-bromopentane, 3: ortho-xylene, 4: o-chlorotoluene, 5: 2-octanone, 6:1,2, 3-trimethylbenzene, 7: m-dichlorobenzene, 8: 1-octanol, 9: methyl octanoate, 10: o-toluidine, 11: n-dodecane, 12:1,3, 5-trichlorobenzene, 13:2, 6-dimethylaniline, 14:2, 3-xylenol, 15: n-tridecane, 16: m-chloroaniline, 17: m-chloronitrobenzene, 18: 2-methylnaphthalene, 19: methyl undecanoate, 20: m-bromonitrobenzene, 21: n-pentadecane. As shown in FIG. 8, the capillary gas chromatographic column prepared by the example has good separation effect on 21-component complex mixtures, and has more types of analytes and wider polarity range. Exhibits good properties of DeLP A stationary phase suitable for separating complex mixtures, and the separation effect is superior to that of polysiloxane commercial columns HP-5 and HP-35.
FIG. 9 is a capillary gas chromatography column prepared in the examples for separating benzaldehyde and halobenzene isomers, selected as analytes for separation, including chloronitrobenzene isomers: o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, methylbenzaldehyde isomers: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
FIG. 9 is a chromatogram of the separation control of benzaldehyde isomers and halobenzene isomers from commercial columns HP-5, HP-35 and P6A-C10 by using the capillary gas chromatographic column prepared in the example, as shown in FIG. 9, the capillary gas chromatographic column prepared in the example can effectively separate benzaldehyde and halobenzene isomers, and has an effect superior to that of the capillary gas chromatographic column prepared from polysiloxane commercial columns HP-5, HP-35 and alkyl functionalized column hexaarene.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. An alkyl functionalized hexa-arene for a stationary phase, wherein the alkyl functionalized hexa-arene has the chemical structure:
。
2. a process for the preparation of an alkyl functionalized hexa-arene for stationary phases according to claim 1, characterized in that it comprises the specific steps of:
Step 1, etherifying monohalogenated hydrocarbon: heating 1, 4-benzenediol, 1-bromodecane, potassium hydroxide and ethanol for reaction, cooling, post-treating and purifying to obtain an intermediate (I);
Step 2, friedel-Crafts alkylation: reacting the intermediate (I), 1, 4-p-dichlorobenzyl, aluminum trichloride and methylene dichloride obtained in the step 1 at room temperature, finishing the reaction, performing post-treatment and purifying to obtain an intermediate (II);
Step 3, ring closure: mixing the intermediate (II) obtained in the step 2, paraformaldehyde, boron trifluoride diethyl etherate and dichloromethane, and after the reaction is finished, carrying out post-treatment and purification to obtain DeLP A (III), wherein the prepared DeLP A (III) has uniform particle size distribution on a capillary gas chromatographic column.
3. The method for preparing the alkyl functionalized hexa-arene for stationary phases according to claim 1, characterized in that: the temperature of the heating reaction in the step 1 is 80-85 ℃; the reaction time range is 4.5-5.5 hours; cooling to 25 ℃; the molar ratio of 1, 4-benzenediol to 1-bromodecane was 1.0: 3.0-3.1; the molar ratio of 1, 4-benzenediol to potassium hydroxide is 1.0: 3.0-3.1; recrystallizing during purification, and using ethanol as solvent.
4. The method for preparing the alkyl functionalized hexa-arene for stationary phases according to claim 2, characterized in that: the reaction in the step 2 is carried out at 25 ℃; the reaction time range is 2-3 hours; the molar ratio of 1, 4-p-dichlorobenzyl to intermediate (I) was 1.0: 5.0-5.1; the molar ratio of 1, 4-p-dichlorobenzyl to potassium hydroxide is 1.0: 3.0-3.1; recrystallizing during purification, and petroleum ether in solvent: the volume ratio of dichloromethane was 20:1.
5. The method for preparing the alkyl functionalized hexa-arene for stationary phases according to claim 2, characterized in that: the reaction in the step 3 is carried out at 25-30 ℃; the reaction time range is 4-5 hours; the molar ratio of intermediate (II) to paraformaldehyde is 1.0: 3.0-3.3; the molar ratio of intermediate (II) to boron trifluoride etherate was 1.0: 1.2-1.3; column chromatography is used in purification, and petroleum ether is used in the eluent; the volume ratio of dichloromethane is 10:1.
6. A capillary gas chromatographic column, characterized in that: the alkyl functionalized inclined hexaarene obtained by the preparation method of claim 2 is prepared into a capillary gas chromatographic column by a static method.
7. Use of the capillary gas chromatography column according to claim 6, wherein: the capillary gas chromatographic column can separate substituted benzaldehyde isomer, aniline isomer, halogenated benzene isomer, 8 groups of cis-trans isomers and 21 groups of complex mixtures; wherein,
Substituted benzaldehyde isomers include: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, o-cyanobenzaldehyde, m-cyanobenzaldehyde, p-cyanobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde;
the aniline isomers include: o-iodoaniline, m-iodoaniline, p-iodoaniline;
The halogenated benzene isomers include: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene;
Group 8 cis-trans isomers include: cis-3, 5-trimethylcyclohexane salicylate and trans-3, 5-trimethylcyclohexane salicylate, cis-1, 3-dimethylcyclohexane and trans-1, 3-dimethylcyclohexane, cis-nerol and trans-nerol, cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol, cis-decalin and trans-decalin, cis-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dimethoxytetrahydrofuran, cis-2, 5-dihydro-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dihydro-2, 5-dimethoxytetrahydrofuran;
The 21-component complex mixture comprises: 2-hexanone, 1-bromopentane, o-xylene, o-chlorotoluene, 2-octanone, 1,2, 3-trimethylbenzene, m-dichlorobenzene, 1-octanol, methyl octanoate, o-toluidine, n-dodecane, 1,3, 5-trichlorobenzene, 2, 6-dimethylaniline, 2, 3-xylenol, n-tridecane, m-chloroaniline, m-chloronitrobenzene, 2-methylnaphthalene, methyl undecanoate, m-bromonitrobenzene, n-pentadecane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410059306.8A CN117902959A (en) | 2024-01-16 | 2024-01-16 | Alkyl functionalized hexa-arene used for stationary phase, preparation method thereof, capillary gas chromatographic column and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410059306.8A CN117902959A (en) | 2024-01-16 | 2024-01-16 | Alkyl functionalized hexa-arene used for stationary phase, preparation method thereof, capillary gas chromatographic column and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117902959A true CN117902959A (en) | 2024-04-19 |
Family
ID=90693429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410059306.8A Pending CN117902959A (en) | 2024-01-16 | 2024-01-16 | Alkyl functionalized hexa-arene used for stationary phase, preparation method thereof, capillary gas chromatographic column and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117902959A (en) |
-
2024
- 2024-01-16 CN CN202410059306.8A patent/CN117902959A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114276257B (en) | Preparation and application of amino-functionalized column pentaarene stationary phase | |
| Xu et al. | Phenylacetylene dendrimers by the divergent, convergent, and double-stage convergent methods | |
| Jempty et al. | Iron trichloride/silicon dioxide reacts as oxidant or Lewis acid with phenol ethers | |
| CN108727402B (en) | Oxaspiro bridged ureidopyrimidone compound and synthetic method thereof | |
| CN109752476B (en) | Calixarene derivative stationary phase, capillary gas chromatographic column, preparation and application thereof | |
| EP2970037A1 (en) | Methods for preparing alkylfurans | |
| CN112300178A (en) | Preparation and application of 5-bromoquinazoline derivative | |
| CN110746451B (en) | Dicationic liquid chromatographic stationary phase and preparation method and application thereof | |
| CN109503337B (en) | Triptycene oxygen-containing straight-chain diol functional material, preparation and application thereof | |
| CN115108930A (en) | Synthetic method and application of aminophenyl benzamide compound | |
| Baciocchi et al. | Substituent effects on intramolecular selectivity and free energy relationships in anodic and metal-ion oxidations of 5-substituted 1, 2, 3-trimethylbenzenes | |
| CN112300107B (en) | Triptycene functional material, preparation method and application thereof | |
| Fox et al. | Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes | |
| Casiraghi et al. | Selective step-growth phenol-aldehyde polymerization. 3. Synthesis, characterization, and x-ray analysis of regular all-ortho ethylidene-linked oligonuclear phenolic compounds | |
| CN117902959A (en) | Alkyl functionalized hexa-arene used for stationary phase, preparation method thereof, capillary gas chromatographic column and application thereof | |
| Casiraghi et al. | Selective step‐growth phenol‐aldehyde polymerization, 2. Synthesis of 4‐tert‐butylphenol novolac resins and related open chain oligomeric compounds | |
| CN115073259B (en) | Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof | |
| Hibert et al. | Substituent effect during the synthesis of substituted [2.2] paracyclophane by photoextrusion of carbon dioxide from a cyclic diester | |
| CN115636737B (en) | Alkyl functionalized column hexaarene stationary phase, capillary gas chromatographic column, and preparation methods and applications thereof | |
| Yip et al. | Transition metal promoted reactions. 29.(Z)-2, 2'-Disubstituted bifluorenylidenes by intramolecular desulfurdimerization reactions | |
| CN112939751B (en) | Fluoren aromatic hydrocarbon macrocycle, preparation method thereof and application thereof in construction of functional conjugated band-shaped compound | |
| Lei et al. | The dimer of unsubstituted silole | |
| CN111675591B (en) | Synthetic method of benzophenanthrene compound | |
| He et al. | Polysiloxanes-based stationary phases containing methoxy-substituted tetraphenyl–phenyl groups for gas chromotographic separations | |
| CN110304982B (en) | Pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement function and synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |