CN116903541B - 用于酚类污染物检测的酰基咪唑类化合物、制备方法及应用 - Google Patents
用于酚类污染物检测的酰基咪唑类化合物、制备方法及应用 Download PDFInfo
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- CN116903541B CN116903541B CN202311014420.0A CN202311014420A CN116903541B CN 116903541 B CN116903541 B CN 116903541B CN 202311014420 A CN202311014420 A CN 202311014420A CN 116903541 B CN116903541 B CN 116903541B
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 66
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- -1 Acyl imidazole compound Chemical class 0.000 title claims abstract description 35
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 23
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000356 contaminant Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
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- XDEPVFFKOVDUNO-UHFFFAOYSA-N pentafluorobenzyl bromide Chemical compound FC1=C(F)C(F)=C(CBr)C(F)=C1F XDEPVFFKOVDUNO-UHFFFAOYSA-N 0.000 description 11
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
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- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- MYHOHFDYWMPGJY-UHFFFAOYSA-N pentafluorobenzoyl chloride Chemical compound FC1=C(F)C(F)=C(C(Cl)=O)C(F)=C1F MYHOHFDYWMPGJY-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- XETRHNFRKCNWAJ-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl 2,2,3,3,3-pentafluoropropanoate Chemical compound FC(F)(F)C(F)(F)C(=O)OC(=O)C(F)(F)C(F)(F)F XETRHNFRKCNWAJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 229960002217 eugenol Drugs 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 239000012074 organic phase Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- 229960003500 triclosan Drugs 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- RZYHXKLKJRGJGP-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)N([Si](C)(C)C)C(=O)C(F)(F)F RZYHXKLKJRGJGP-UHFFFAOYSA-N 0.000 description 1
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- JTOIZLCQNWWDCN-UHFFFAOYSA-N 2,4-bis(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(C(F)(F)F)C=C1C(F)(F)F JTOIZLCQNWWDCN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical class C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- XPDXVDYUQZHFPV-UHFFFAOYSA-N Dansyl Chloride Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1S(Cl)(=O)=O XPDXVDYUQZHFPV-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 206010023644 Lacrimation increased Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010067572 Oestrogenic effect Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
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- WBKFWQBXFREOFH-UHFFFAOYSA-N dichloromethane;ethyl acetate Chemical compound ClCCl.CCOC(C)=O WBKFWQBXFREOFH-UHFFFAOYSA-N 0.000 description 1
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- UFFSXJKVKBQEHC-UHFFFAOYSA-N heptafluorobutyric anhydride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OC(=O)C(F)(F)C(F)(F)C(F)(F)F UFFSXJKVKBQEHC-UHFFFAOYSA-N 0.000 description 1
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- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/52—Physical parameters
- G01N30/54—Temperature
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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Abstract
本发明公开了用于酚类污染物检测的酰基咪唑类化合物,其用于酚类污染物监测中具有稳定性好、反应灵敏度高、基质干扰小、检出限低、分析时间短、快速检测、准确定量的优点。本发明还公开了用于酚类污染物检测的酰基咪唑类化合物的制备方法,其从已知可得的原料出发,一步法即可得到GC‑MS/MS检测的土壤、水体、大气环境中酚类污染物的新型化合物。本发明的酰基咪唑类化合物可作为衍生化试剂用于酚类污染物的检测,其衍生化反应的副产物咪唑对色谱柱无影响,相比于现有衍生化试剂能更好地保护色谱柱的寿命,另外,由于咪唑的存在,其可充当碱,无需添加外源碱,或者只需加入催化量碱,即可进一步催化衍生反应的正向进行,有力提升反应转化率。
Description
技术领域
本发明涉及酚类污染物检测技术领域,具体涉及用于酚类污染物检测的酰基咪唑类化合物、制备方法及应用。
背景技术
作为合成树脂、焦化炼油、木材防腐等化工基本原料,酚类化合物的广泛使用给生态环境、动植物和人体健康带来严重危害。苯酚、2, 4, 6-三氯酚、五氯酚等物质被确定为优先控制污染物;双酚A(bisphenol,BPA) 和烷基酚类化合物(alkylphenol compounds,APs)等被广泛应用于塑料、橡胶、涂料、液晶、洗涤剂等领域。作为典型的环境内分泌干扰物,BPA和APs具有***效应, 通过干扰人体内分泌物质的合成、运输及代谢过程来破坏生理平衡,影响人体生殖、免疫神经等功能,被欧美国家列入重点管控的新污染物清单。
目前,酚类化合物一般采用气相色谱、液相色谱、气相色谱-质谱联用等方法进行测定。HPLC直接紫外或者荧光检测的灵敏度差,基质干扰严重,往往无法实现实际样品的准确检测;对于复杂生物基质或环境样本中的微量酚类物质,其样本在HPLC-MS检测的离子化效率低,检测不灵敏,基质抑制和无机盐及内源性杂质的干扰严重。同时,由于酚类化合物属于极性较强的半挥发性物质,直接用GC-MS检测时响应系数低,检出限较高,不能达到检测痕量浓度的目的。而通过化学衍生方法,使目标物转化为易挥发的非极性化合物,能够改善酚类化合物的理化性质和色谱行为,有效提高检测灵敏度。
目前常见的酚类衍生化方法包括:
(1)酰化衍生:多采用乙酸酐、三氟乙酸酐、五氟丙酸酐、苯甲酰氯、五氟苯甲酰氯(PFBOCl)、七氟丁酸酐等作为衍生试剂;
(2)烷基化衍生:试剂主要为重氮甲烷、五氟苄基溴(PFBBr);
(3)硅烷基化衍生:常用试剂为N,O-双(三甲基硅烷基)三氟乙酰胺(含1%三甲基氯硅烷(BSTFA-TMCS)溶液;
(4)溴化反应:采用酸性条件下KBr-KBrO3溶液为衍生化试剂。
如文献“Peng X,Wang Z,Yang C,et al.Simultaneous determination ofendocrine -disrupting phenols and steroidestrogens in sediment by gaschromatography-mass spectrometry [J].Journal of chromatography A, 2006,1116(1-2): 51-56”中运用五氟丙酸酐对珠江河口处沉积物中的环境内分泌干扰物进行衍生化,通过提取方法和衍生条件的优化,能够完成沉积物中含量在1 ng·g-1以下的目标物测定,且回收率良好。发明专利“赵汝松,苑金鹏,王霞等,环境水样中三氯生的快速分析方法(CN101158671[P].2008)”公开了一种应用三氟乙酸酐作为衍生化试剂快速分析环境水样中三氯生的方法,该方法具有简便、快速、分析准确、样品前处理时间短等优点。
文献“程聪,王鑫,刘有平等,柱前衍生化LC-MS/MS法测定大鼠血浆中丁香酚的质量浓度[J]。沈阳药科大学学报,2021,38(3):251-257”中记载以麝香草酚为内标,血浆样品经丹磺酰氯衍生化,建立灵敏的柱前衍生化LC-MS/MS方法测定大鼠血浆中丁香酚含量。文献“崔连喜,王艳丽,加速溶剂萃取-五氟苄基衍生化-气相色谱/质谱法测定土壤中酚类化合物[J]。中国测试,2020,46(11):59-64”中采用五氟苄基进行酚烷基化测定土壤中酚类物质,该方法灵敏度高,定性准确,能够满足不同类型土壤中多种酚类化合物的检测要求。文献“周同娜,尹海亮,固相萃取-衍生化-气相色谱-质谱法同时测定环境水中双酚A和9种烷基酚类化合物的含量[J]。理化检验-化学分册,2022,58(10): 1182-1188”中采用三甲基氯硅烷进行硅烷基化衍生,测定水中双酚A和9种APs,方法检出限低,重现性良好。
同时,在环保部标准HJ 703-2014《土壤和沉积物酚类化合物的测定气相色谱法》、HJ744-2015《水质酚类化合物的测定气相色谱-质谱法》和HJ834-2017《土壤和沉积物半挥发性有机物的测定气相色谱-质谱法》附录B.2硅胶净化酚类化合物等标准中均涉及到五氟苄基溴等衍生化试剂的使用。
尽管上述各类衍生试剂不同程度地提高了酚类物质的色谱响应值,但是在衍生效率、稳定性、反应终点等方面,现有技术仍存在以下亟待解决的问题:
(1)衍生试剂三甲基硅衍生物自身不稳定、易分解;
(2)酰氯或者酸酐在测试水体样品时极易水解,难以实现定量检测;
(3)酰氯、五氟苯甲酰氯等对眼睛、皮肤粘膜和呼吸道有强烈刺激性;五氟苄基溴对人体皮肤粘膜有腐蚀作用,对眼睛有催泪效应和强烈的腐蚀性。
(4)酰化、溴代、烷基化等衍生反应的副产物为氯化氢、溴化氢、磺酸等强酸,对色谱柱存在不可逆损伤;
(5)部分衍生试剂的衍生化时间较长,检测速度缓慢,难以达到反应终点,不利于快速准确检测。
同时,环境中双酚A和APs等新污染物的实际样品通常含量较低,组分复杂,且干扰物质较多,因此开发高灵敏度、高选择性、稳定性好、能快速到达反应终点,且副产物对色谱柱无损伤的酚类衍生化试剂成为解决前述问题的关键方案。
发明内容
本发明的一个目的是解决至少上述问题和/或缺陷,并提供至少后面将说明的优点。
本发明还有一个目的是提供一种用于酚类污染物检测的酰基咪唑类化合物,其易与酚类化合物进行反应,可作为衍生化试剂用于酚类污染物的检测,具有稳定性好、反应灵敏度高、基质干扰小、检出限低、分析时间短、快速检测、准确定量的优点。
本发明还有另外一个目的是提供一种制备用于酚类污染物检测的酰基咪唑类化合物的方法,其从已知可得的原料出发,通过一步反应成功合成了可用于土壤、水体、大气环境中酚类污染物的新型化合物。
本发明还有另外一个目的是提供了用于酚类污染物检测的酰基咪唑类化合物作为酚类衍生化试剂在土壤、水体、大气环境中酚类污染物检测中的应用。
为了实现根据本发明的这些目的和其它优点,提供了一种用于酚类污染物检测的酰基咪唑类化合物,其具有如下式(I)的结构:
(I)
其中,R1、R2、R3、R4独立地为H、 CF3、 NO2、F、Cl或Br。
优选的是,其中,R2为CF3,R1、R3、R4均为H。
优选的是,其中,R2为NO2,R1、R3、R4均为H。
本发明的目的还可以进一步由用于酚类污染物检测的酰基咪唑类化合物的制备方法来实现,其以如下式(II)化合物为原料,溶于有机溶剂中,与N,N'-羰基二咪唑一步反应后纯化即可得到式(I)化合物;
(II)。
优选的是,其中,式(II)化合物与N,N'-羰基二咪唑的摩尔比为1:1~1:1.2。
优选的是,其中,反应温度为室温,反应时间为1~3 h。
优选的是,其中,所有机溶剂为四氢呋喃。
优选的是,其中,纯化具体包括:减压旋除有机溶剂,中性氧化铝拌样,硅胶柱层析分离纯化,其中,柱层析所用洗脱剂为体积比为5:1的石油醚和乙酸乙酯。
本发明的目的还可以进一步由用于酚类污染物检测的酰基咪唑类化合物作为酚类衍生化试剂的应用来实现。
本发明至少包括以下有益效果:
1、本发明用于酚类污染物检测的酰基咪唑化合物通过调整芳环母核骨架上的取代基诱导效应,对强拉电子基团的取代位置和取代基数目进行优化,优选2位CF3取代为化合物稳定性良好位次,硝基的引入会一定程度降低衍生试剂的稳定性,合成得到稳定性明显优于酰氯、酸酐及苄溴等衍生化试剂的新型酰基咪唑活性化合物。
2、本发明的用于酚类污染物检测的酰基咪唑类化合物,在保持其自身稳定性的前提下,向分子中引入不同种类和数量的强拉电子基团,最大程度地提升衍生试剂对底物样品的反应灵敏度,大幅提高质谱响应效率的制备方法,反应原料易得,合成条件简单,制备产率高,所得产物易于离子化。
3、本发明的用于酚类污染物检测的酰基咪唑类化合物作为酚类衍生化试剂与酚类化合物发生衍生反应的副产物为咪唑,该小分子对色谱柱无影响,极大改进了现有技术的普遍难题,更好地保护了色谱柱的寿命。既往酰化、烷基化、溴代等衍生反应的副产物为氯化氢、溴化氢、甲磺酸等强酸,对色谱柱的损伤程度大。
4、本发明的用于酚类污染物检测的酰基咪唑类化合物作为酚类衍生化试剂与酚发生衍生反应生成的咪唑可充当碱的作用,进一步催化衍生反应的正向进行,有力提升反应转化率。
5、由于本发明的用于酚类污染物检测的酰基咪唑类化合物作为酚类衍生化试剂与酚发生衍生反应生成的咪唑的存在,可以不需要添加外源碱,或者只需加入催化量碱,即可促进反应快速达到终点,实现对酚类物质的准确定量。
6、本发明的用于酚类污染物检测的酰基咪唑类化合物作为酚类衍生化试剂对实际样品进行GC-MS检测,该检测方法具有衍生试剂稳定性好,反应灵敏高、基质干扰小、检出限低、分析时间短、能够快速达到检测终点、准确定量的优点。
7、本发明的用于酚类污染物检测的酰基咪唑类化合物的制备方法从已知可得的原料出发,通过一步合成获得可用于GC-MS/MS检测的土壤、水体、大气环境中酚类污染物的新型化合物。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1为本发明实施例1中化合物BTFBZI的核磁共振氢谱图;
图2为本发明实施例1中化合物BTFBZI的核磁共振碳谱图;
图3为本发明实施例2中化合物pNTFBZI的核磁共振氢谱图;
图4为本发明实施例2中化合物pNTFBZI的核磁共振碳谱图;
图5为本发明实施例3中化合物1的核磁共振氢谱图;
图6为本发明实施例3中化合物1的核磁共振碳谱图;
图7为本发明实施例4中化合物2的核磁共振氢谱图;
图8为本发明实施例4中化合物2核磁共振碳谱图;
图9为本发明实施例4中化合物3的核磁共振氢谱图;
图10为本发明实施例4中化合物3的核磁共振氢谱图;
图11为本发明实施例5中化合物4的核磁共振氢谱图;
图12为本发明实施例5中化合物4的核磁共振氢谱图;
图13为本发明实施例6中化合物5的核磁共振氢谱图;
图14为本发明实施例6中化合物5的核磁共振氢谱图;
图15为本发明实施例6中化合物6的核磁共振氢谱图;
图16为本发明实施例6中化合物6的核磁共振氢谱图;
图17为本发明实施例7中化合物7的核磁共振氢谱图;
图18为本发明实施例7中化合物7的核磁共振氢谱图;
图19为本发明实施例9中BTFBZI、苯酚-BTFBZI产物的总离子流谱图;
图20为本发明实施例9中BTFBZI、双酚A-BTFBZI产物的总离子流谱图。
具体实施方式
下面结合附图对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
应当理解,本文所使用的诸如“具有”、“包含”以及“包括”术语并不配出一个或多个其它元件或其组合的存在或添加。
需要说明的是,下述实施方案中所述实验方法,如无特殊说明,均为常规方法,所述试剂和材料,如无特殊说明,均可从商业途径获得。
<实施例1>
用于酚类污染物检测的酰基咪唑类化合物(2, 4-双(三氟甲基)-苯基) (1H-咪唑基)甲酮(BTFBZI),其结构式如下:
具体合成路线如下:
具体合成步骤如下:
冰浴条件下,将2, 4-双三氟甲基苯甲酸(517 mg,2.0 mmol)溶于四氢呋喃(15mL)中充分溶解,逐滴加入N,N'-羰基二咪唑CDI(341 mg,2.1 mmol)的四氢呋喃溶液(5mL),加完之后反应体系升至室温反应,TLC监测,1.0 h后原料完全消耗。停止反应后,旋除溶剂,中性氧化铝拌样柱层析(石油醚/乙酸乙酯 5/1)分离得到白色固体产品(540 mg,产率87.7%)。MS (m/z, %): 308(M+, 100);1H NMR (300 MHz, DMSO-d 6) δ 8.33 (m, 2H),8.19 (m, 2H), 7.71 (s, 1H), 7.19 (s, 1H).13C NMR (75 MHz, DMSO-d 6) δ 163.89,139.16, 134.97, 131.80, 130.97, 127.92, 124.71, 118.07, 42.00-40.98,41.06-40.12, 39.98, 39.84-38.92, 38.92-38.14.
化合物BTFBZI的核磁共振氢谱见图1,核磁共振碳谱见图2。
<实施例2>
用于酚类污染物检测的酰基咪唑类化合物 (1H-咪唑基)(4-硝基-2-三氟甲基-苯基)甲酮(pNTFBZI),其结构式如下:
具体合成路线如下:
具体合成步骤同实施例1,得到白色固体产品(产率91.2%)。MS (m/z, %): 285 (M+, 100);1H NMR (300 MHz, DMSO-d 6) δ 8.69 (s, 1H), 8.46 (d, J = 8.0 Hz, 1H),8.26 (d, J = 7.6 Hz, 2H), 7.75 (s, 1H),7.20-7.14 (m, 1H).13C NMR (75 MHz,DMSO-d 6) δ 163.07, 146.21, 138.66, 135.32, 132.93-132.35, 131.76, 131.48,123.15, 121.35, 117.80.
化合物pNTFBZI的核磁共振氢谱见图3,核磁共振碳谱见图4。
<实施例3>
实施例1中化合物BTFBZI与苯酚反应合成衍生产物。
与苯酚反应所得衍生产物具有如下结构:
具体合成路线:
合成步骤:
将化合物BTFBZI(155 mg,0.5 mmol)溶于四氢呋喃(10 mL)中,加入苯酚(70 mg,0.75 mmol)和三乙胺(5 mg,0.05 mmol),室温反应,TLC监测,5 min以内原料完全消耗。停止反应后,旋除溶剂,快速柱层析(石油醚/乙酸乙酯 10/1)分离得到白色固体3(142 mg,产率85.0%)。MS (m/z, %): 334 (M+, 100);1H NMR (300 MHz, DMSO-d 6) δ 8.35 (dd, J =15.9, 10.1 Hz, 3H), 7.53 (t, J = 7.7 Hz, 2H), 7.36 (dd, J = 16.8, 7.6Hz, 3H).13C NMR (75 MHz, DMSO-d 6) δ 164.19, 150.44, 134.14, 132.95, 132.40, 130.60,130.47-129.99, 128.72, 128.28, 127.11, 124.90, 124.36, 121.99-121.54, 121.27.化合物1的核磁共振氢谱见图5,核磁共振碳谱见图6。
<实施例4>
实施例1中化合物BTFBZI与双酚A反应合成衍生产物。
与双酚A反应所得衍生产物具有如下结构:
和
具体合成路线:
合成步骤:
将化合物BTFBZI(770 mg,2.5 mmol)溶于四氢呋喃(10 mL)中,加入双酚A(228mg,1 mmol)和三乙胺(5 mg,0.05 mmol),室温反应,TLC监测,10 min以内原料完全消耗。停止反应后,旋除溶剂,快速柱层析(石油醚/乙酸乙酯 15/1-5/1)分离得到化合物2(双酚酯,白色固体572 mg, 80.8%)和化合物3(单酚酯,白色固体16 mg,产率16.9%)。化合物2:MS(m/z, %): 708 (M+, 100); 1H NMR (300 MHz, DMSO-d 6) δ 8.32 (d, J = 10.7 Hz,6H), 7.39 (d, J = 8.5 Hz, 4H), 7.25 (d, J = 8.5 Hz, 4H), 1.71 (s, 6H).13C NMR(75 MHz, DMSO-d 6) δ 164.28, 148.89, 148.35, 134.18, 132.94, 132.38, 130.72,128.68, 128.31, 125.03, 124.48,121.35, 42.69, 40.83, 40.55, 40.27, 39.99,39.71, 39.44, 39.16, 30.89.
化合物3:MS (m/z, %): 468 (M+, 100); 1H NMR (300 MHz, DMSO-d 6) δ 9.20(s, 1H), 8.31 (d, J = 9.0 Hz, 3H),7.33 (d, J = 8.6 Hz, 2H), 7.20 (d, J = 8.5Hz, 2H), 7.04 (d, J = 8.5 Hz, 2H), 6.69 (d, J = 8.4 Hz, 2H), 1.62 (s, 6H).13C NMR (75 MHz, DMSO-d 6) δ 164.32, 155.66, 149.83, 148.10, 140.59,132.25,128.26, 127.84, 121.10, 115.23, 42.03, 40.84, 40.68, 40.12, 39.57, 39.15,31.10.
化合物2的核磁共振氢谱见图7,核磁共振碳谱见图8。化合物3的核磁共振氢谱见图9,核磁共振碳谱见图10。
<实施例5>
实施例2中化合物pNTFBZI与苯酚反应合成衍生产物。
与苯酚反应所得衍生产物具有如下结构:
具体合成路线:
合成步骤同实施例3,得到化合物4。MS (m/z, %): 311 (M+, 100); 1H NMR (300MHz, DMSO-d 6) δ 8.71 (dd, J = 8.5, 2.1 Hz, 1H), 8.63 (d, J = 2.0 Hz, 1H),8.42 (d, J = 8.5 Hz, 1H), 7.53 (t,J = 7.8 Hz, 1H), 7.36 (dd, J = 15.8, 7.5Hz, 1H). 13C NMR (75 MHz, DMSO-d 6) δ 163.86, 163.01, 150.36, 149.59, 148.14,135.46, 132.97, 132.15, 130.32, 128.91, 128.43, 127.22, 122.61, 121.75.
化合物4的核磁共振氢谱见图11,核磁共振碳谱见图12。
<实施例6>
实施例2中化合物pNTFBZI与双酚A反应合成衍生产物。
与双酚A反应所得衍生产物具有如下结构:
和
具体合成路线:
合成步骤同实施例4,得到双酚酯化合物5和单酚酯化合物6。
化合物5:MS (m/z, %): 662 (M+, 100); 1H NMR (300 MHz, DMSO-d 6) δ 8.70(d, J = 8.4 Hz, 2H), 8.63 (s, 2H), 8.40 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.6Hz, 4H), 7.26 (d, J = 8.5 Hz, 4H), 1.71 (s, 6H). 13CNMR (75 MHz, DMSO-d 6) δ163.95, 149.64, 148.97, 148.30, 135.51, 132.95, 128.88, 128.46, 124.62,122.69,121.35, 42.72, 40.83, 40.56, 40.28, 40.00, 39.72, 39.46, 39.30, 30.90.
化合物5的核磁共振氢谱见图13,核磁共振碳谱见图14。
化合物6:MS (m/z, %): 445 (M+, 100); 1H NMR (300 MHz, DMSO-d 6) δ 9.22(s, 1H), 8.71 (dd, J = 8.5, 2.2 Hz, 1H), 8.63 (d, J = 2.1 Hz, 1H), 8.39 (d, J= 8.5 Hz, 1H), 7.36-7.29 (m, 2H), 7.25-7.18 (m, 2H),7.08-6.99 (m, 2H), 6.73-6.64 (m, 2H), 1.62 (s, 6H). 13C NMR (75 MHz, DMSO-d 6) δ 163.99, 155.65,149.92, 149.63, 148.04,140.58, 132.93, 128.39, 127.84, 122.65, 121.09,115.24, 42.05, 40.84, 40.56, 40.28, 40.01, 39.73, 39.45, 39.17, 31.11.
化合物6的核磁共振氢谱见图15,核磁共振碳谱见图16。
<实施例7>
衍生产物7的合成方法同实施例3(注:分离过程中未获得稳定存在的化合物oNTFBZI)。化合物7: MS (m/z, %): 311 (M+, 100);1H NMR (300 MHz, DMSO-d 6) δ 8.60(s, 1H), 8.37 (s, 1H), 7.53 (t, J = 7.8 Hz, 1H), 7.40-7.28 (m, 2H). 13C NMR(75 MHz, DMSO-d 6) δ 163.01, 150.35, 148.15, 133.48, 133.03, 132.15, 131.31,130.28, 129.88, 127.19, 124.76, 122.92-122.05, 121.72, 121.14.
化合物7的核磁共振氢谱见图17,核磁共振碳谱见图18。
衍生产物生成机理:
酚类衍生产物的生成机理包括如下三步:
(1)N,N'-羰基二咪唑与羧酸发生亲核加成消去反应,脱除副产物咪唑;
(2)咪唑充当碱催化作用,进一步亲核进攻酸酐中间体,离去另一分子的咪唑,同时脱除一分子二氧化碳,得到酰基咪唑稳定中间体;
(3)酚类化合物的酚羟基亲核进攻酰基咪唑中间体的羰基,脱除咪唑小分子,得到酚酯衍生物,达到反应终点。
<实施例8>
用于酚类污染物检测的酰基咪唑类化合物的稳定性评价。
,/>,/>
对上述三种作为酚类衍生试剂的稳定性进行分析,结果发现,硝基引入芳环后,化合物pNTFBZI和oNTFBZI的稳定性降低,其中化合物oNTFBZI在分离过程中不能稳定存在,容易分解;而化合物pNTFBZI的稳定性相对较好,表明硝基处于酰基咪唑的对位时,对衍生试剂的稳定性影响相对较小。TLC持续监测发现,化合物pNTFBZI可以在72小时内稳定存在,而化合物BTFBZI的晶体可以在6周内持续稳定存在(通过薄层色谱持续监测,展开剂石油醚/乙酸乙酯=2/1),因此,化合物BTFBZI适合被开发为高选择性、高灵敏度、稳定性良好的酚类衍生化试剂。
<实施例9>
化合物BTFBZI检测水质中的苯酚和双酚A:
1、苯酚-BTFBZI、双酚A-BTFBZI标准溶液配制:
1.1、BTFBZI衍生溶液ρ=500 μg/mL的配制:
将5 mgBTFBZI加入二氯甲烷中,定容至10 mL,配制成500 μg/mL的BTFBZI衍生溶液。
1.2、苯酚-BTFBZI标准溶液配制:
分别取1 mL的100、200、500、1000、2000、5000 μg/L的苯酚标准溶液,加入20 μL三乙胺、100 μL 500 μg/mL的BTFBZI溶液,常温下静置3 h,配制成苯酚-BTFBZI标准溶液。
1.3、双酚A-BTFBZI标准溶液的配制:
分别取1 mL的100、200、500、1000、2000、5000 μg/L的双酚A标准溶液,加入20 μL三乙胺、100 μL500 μg/mL的BTFBZI溶液,常温下静置3 h,配制成双酚A-BTFBZI标准溶液。
2、BTFBZI检测水质中的苯酚、双酚A前处理:
向200 mL水样中加入20 mL二氯甲烷-乙酸乙酯(V/V=1:1),振荡3 min后静置至水相和有机相充分分离,收集有机相,并经过无水硫酸钠脱水。重复2次上述萃取步骤, 用旋蒸、氮吹浓缩至1 mL,加入20 μL三乙胺、100 μL 500 μg/mL的BTFBZI衍生溶液,常温静置3h,待测。
3、仪器条件:
气相色谱条件:
进样口:290℃;分流比:10:1 柱流量:1.2 mL/min;
升温程序:35℃(4 min),40 ℃/min升至170℃,15℃/min升至310℃(3min);
色谱柱:DB-5MS 30 m × 0.25 mm × 0.25 μm;
质谱条件:
传输线温度:290℃;离子源温度:230℃;四极杆温度:150℃;
离子源电子能量:70eV;数据采集方式:SCAN (m/z:50~600)。
4、目标化合物的保留时间、定量离子、线性方程和相关系数:见表1:
表1标准溶液的保留时间、定量离子、辅助离子和线性方程
/>
BTFBZI、苯酚-BTFBZI产物的总离子流谱图见图19;BTFBZI、双酚A-BTFBZI产物的总离子流谱图见图20。
<对比例1>
五氟苄基溴是常用于环境样品中酚类化合物检测的衍生化试剂,《水质 酚类化合物的测定气相色谱-质谱法》( HJ 744-2015)和 《土壤和沉积物半挥发性有机物的测定 气相色谱-质谱法》( HJ 834-2017)中均采用五氟苄基溴对酚类化合物进行衍生,衍生产物通过气相色谱-质谱进行检测,以达到酚类目标物定量分析的目的。传统衍生试剂五氟苄基溴属于催泪性物质毒性较大、衍生过程中需要加入无机盐催化剂(碳酸钾)对气相色谱柱极不友好。尽管气相色谱质谱法具有定量准确,重现性好的优点,但是由于传统衍生产物的灵敏度较低,因而只适于检测环境样品中浓度相对较高的酚类化合物;同时传统方法回收率差,准确度偏低;此外,使用五氟苄基溴衍生-气相色谱质谱法测定环境样品中的酚类化合物,具有前处理繁琐,需要的配制的前处理溶液多,反应对温度要求高,不利于低浓度样品的高效检测。
现有技术中用于环境样品中酚类化合物检测的衍生化试剂化合物五氟苄基溴与本发明的BTFBZI化合物用于酚类化合物检测的对比数据如下表2。
表2 五氟苄基溴与BTFBZI检测酚类化合物的对比
衍生化试剂 | BTFBZI | 五氟苄基溴 |
理化性质 | 白色无味。 | 催泪物质,对实验人员身体伤害大。 |
检测方法 | GCMS | GCMS |
检出限(μg/L) | 0.02 | 0.1(HJ744-2015) |
衍生温度 | 常温 | 60°C |
衍生化条件 | 1 mL样品中加入20 μL三乙胺、100 μL 500μg/mL的BTFBZI溶液,常温反应3 h。 | 8 mL样品中分别加入100 μL的五氟苄基溴和0.1 g/mL碳酸钾溶液,60°C衍生60 min,将溶剂体系更换至正己烷,浓缩定容至1mL。 |
回收率 | 95.7%~99.4% | 82.5%~87.5 |
由上表2可以看出,现有技术中用于环境样品中酚类化合物检测的五氟苄基溴,衍生化产物毒性较大、衍生过程中需要加入无机盐催化剂对色谱柱不友好,一般采用气相色谱-质谱法进行检测。尽管气相色谱质谱法具有定量准确,重现性好的优点,但是由于其灵敏度较低,因而只适于检测土壤样品中浓度相对较高的酚类化合物;同时回收率差。本发明的BTFBZI化合物作为衍生化试剂对检测样品进行GC-MS检测,具有衍生试剂稳定性好,质谱响应高、基质干扰小、检出限低、重现性好、分析时间短、能够快速达到检测终点、准确定量、回收率高的优点。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用。它完全可以被适用于各种适合本发明的领域。对于熟悉本领域的人员而言,可容易地实现另外的修改。因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节和这里示出与描述的图例。
Claims (7)
1.用于酚类污染物检测的酰基咪唑类化合物,其具有如下式(I)的结构:
(I)
其中,R2为CF3或NO2,R1、R3、R4均为H。
2.一种制备权利要求1所述的用于酚类污染物检测的酰基咪唑类化合物的方法,其以如下式(II)化合物为原料,溶于有机溶剂中,与N, N'-羰基二咪唑一步反应后纯化即可得到式(I)化合物;
(II);
其中,R2为CF3或NO2,R1、R3、R4均为H。
3.如权利要求2所述的方法,其中,式(II)化合物与N, N'-羰基二咪唑的摩尔比为1:1~1:1.2。
4.如权利要求2所述的方法,其中,反应温度为室温,反应时间为1~3 h。
5.如权利要求2所述的方法,其中,有机溶剂为四氢呋喃。
6.如权利要求2所述的方法,其中,纯化具体包括:减压旋除有机溶剂,中性氧化铝拌样,硅胶柱层析分离纯化,其中,柱层析所用洗脱剂为体积比为5:1的石油醚和乙酸乙酯。
7.权利要求1所述的用于酚类污染物检测的酰基咪唑类化合物作为酚类衍生化试剂的应用。
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