CN116903541B - Acyl imidazole compound for detecting phenolic pollutants, preparation method and application - Google Patents

Acyl imidazole compound for detecting phenolic pollutants, preparation method and application Download PDF

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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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CN116903541A (en
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汪素芳
曹莹
董淮晋
高存富
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Chinese Research Academy of Environmental Sciences
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Abstract

The invention discloses an acyl imidazole compound for detecting phenolic pollutants, which has the advantages of good stability, high reaction sensitivity, small matrix interference, low detection limit, short analysis time, rapid detection and accurate quantification when being used for monitoring the phenolic pollutants. The invention also discloses a preparation method of the acyl imidazole compound for detecting the phenolic pollutants, which is characterized in that the novel compound of the phenolic pollutants in soil, water and atmospheric environment detected by GC-MS/MS can be obtained by a one-step method from the known available raw materials. The acyl imidazole compound can be used as a derivatization reagent for detecting phenolic pollutants, the byproduct imidazole of the derivatization reaction has no influence on a chromatographic column, and compared with the existing derivatization reagent, the service life of the chromatographic column can be better protected, in addition, the acyl imidazole compound can serve as alkali without adding exogenous alkali or only adding catalytic amount of alkali, so that the forward direction of the derivatization reaction can be further catalyzed, and the reaction conversion rate is greatly improved.

Description

Acyl imidazole compound for detecting phenolic pollutants, preparation method and application
Technical Field
The invention relates to the technical field of phenolic pollutant detection, in particular to an acyl imidazole compound for phenolic pollutant detection, a preparation method and application thereof.
Background
As basic chemical raw materials for synthetic resin, coking oil refining, wood preservation and the like, the wide use of phenolic compounds brings serious harm to ecological environment, animals, plants and human health. Phenol, 2, 4, 6-trichlorophenol, pentachlorophenol, etc. are identified as the priority controlling contaminants; bisphenol a (BPA) and alkylphenol compounds (alkylphenol compounds, APs) and the like are widely used in the fields of plastics, rubber, paint, liquid crystal, detergents and the like. As typical environmental endocrine disruptors, BPA and APs have estrogenic effects, disrupt physiological balance by interfering with synthesis, transport and metabolic processes of human endocrine substances, affect functions of human reproduction, immune nerves and the like, and are listed in new pollutant lists which are controlled by the european and american countries.
At present, the phenolic compounds are generally measured by adopting methods such as gas chromatography, liquid chromatography, gas chromatography-mass spectrometry and the like. The sensitivity of HPLC direct ultraviolet or fluorescence detection is poor, the matrix interference is serious, and the accurate detection of an actual sample cannot be realized often; for trace phenols in complex biological matrix or environmental samples, ionization efficiency of the samples in HPLC-MS detection is low, detection is insensitive, and interference of matrix inhibition and inorganic salts and endogenous impurities is serious. Meanwhile, because the phenolic compound belongs to a semi-volatile substance with stronger polarity, the response coefficient is low when the GC-MS is directly used for detection, the detection limit is higher, and the aim of detecting trace concentration cannot be fulfilled. The chemical derivatization method converts the target into a volatile nonpolar compound, so that the physicochemical property and chromatographic behavior of the phenolic compound can be improved, and the detection sensitivity can be effectively improved.
Current common methods of phenol derivatization include:
(1) Acylation derivatization: acetic anhydride, trifluoroacetic anhydride, pentafluoropropionic anhydride, benzoyl chloride, pentafluorobenzoyl chloride (PFBOCl), heptafluorobutyric anhydride and the like are mainly used as derivative reagents;
(2) Alkylation derivatization: the reagent is mainly diazomethane and pentafluorobenzyl bromide (PFBBr);
(3) Silylation derivatization: the common reagents areN,OBis (trimethylsilyl) trifluoroacetamide (1% trimethylchlorosilane (BSTFA-TMCS) in solution;
(4) Bromination reaction: KBr-KBrO under acidic condition 3 The solution is a derivatizing agent.
For example, in the literature "Peng X, wang Z, yang C, et al Simultaneous determination of endocrine-disrupting phenols and steroidestrogens in sediment by gas chromatography-mass spectrometry [ J ]].Journal of chromatography A2006,1116 (1-2): 51-56' in which the environmental endocrine disruptors in the sediment at the mouth of the pearl river are derivatized with pentafluoropropionic anhydride, the content of the sediment being 1 ng g can be achieved by optimizing the extraction method and the derivatization conditions -1 The following target was measured, and the recovery rate was good. Invention patent Zhao Rusong, yuan jin Peng, wang Xia, etc., rapid analysis method of triclosan in environmental water sample (CN 101158671[ P ]]2008) discloses a method for rapidly analyzing triclosan in an environmental water sample by using trifluoroacetic anhydride as a derivatization reagent, and the method has the advantages of simplicity, convenience, rapidness, accuracy in analysis, short sample pretreatment time and the like.
The literature "Cheng Cong, wang Xin, liu You is equal and the mass concentration of eugenol in rat plasma is determined by the pre-column derivatization LC-MS/MS method [ J ]. University of Shenyang pharmacy, 2021, 38 (3): 251-257' describes the measurement of eugenol content in rat plasma by using thymol as an internal standard, derivatizing plasma samples with dansyl chloride, and establishing a sensitive pre-column derivatization LC-MS/MS method. Document "Cui Lianxi, wang Yanli, accelerated solvent extraction-pentafluorobenzyl derivatization-gas chromatography/mass spectrometry for determining phenolic compounds in soil [ J ]. Chinese test 2020, 46 (11): 59-64' adopts pentafluorobenzyl to carry out phenol alkylation to determine phenolic substances in soil, and the method has high sensitivity and accurate qualitative performance, and can meet the detection requirements of various phenolic compounds in different types of soil. Document "Zhou Tongna, yin Hailiang, solid phase extraction-derivatization-gas chromatography-mass spectrometry, simultaneously determines the contents of bisphenol a and 9 alkylphenols in ambient water [ J ]. Physicochemical inspection-chemical division 2022, 58 (10): 1182-1188' adopts trimethylchlorosilane for silylation derivatization, and is used for measuring bisphenol A and 9 APs in water, and the method has low detection limit and good reproducibility.
Meanwhile, the use of derivatization reagents such as pentafluorobenzyl bromide and the like is involved in the standards of environmental protection department standard HJ 703-2014 'determination gas chromatography of soil and sediment phenolic compounds', HJ744-2015 'determination gas chromatography-mass spectrometry of water quality phenolic compounds' and HJ834-2017 'determination gas chromatography-mass spectrometry of soil and sediment semi-volatile organic matters' appendix B.2 silica gel purification phenolic compounds and the like.
Although the above various derivatizing agents improve the chromatographic response values of phenols to different degrees, the following problems to be solved in the prior art still exist in terms of derivatization efficiency, stability, reaction endpoint and the like:
(1) The derivative reagent, namely the trimethylsilicon derivative, is unstable and is easy to decompose;
(2) Acyl chloride or anhydride is easy to hydrolyze when a water body sample is tested, and quantitative detection is difficult to realize;
(3) Acyl chloride, pentafluorobenzoyl chloride and the like have strong irritation to eyes, skin mucous membranes and respiratory tracts; pentafluorobenzyl bromide has a corrosive action on human skin mucosa, and has a lacrimation effect and strong corrosiveness on eyes.
(4) The byproducts of the derivative reactions such as acylation, bromination, alkylation and the like are strong acids such as hydrogen chloride, hydrogen bromide, sulfonic acid and the like, and the chromatographic column is irreversibly damaged;
(5) The derivatization time of part of the derivatization reagent is long, the detection speed is slow, the reaction endpoint is difficult to reach, and the rapid and accurate detection is not facilitated.
Meanwhile, the actual samples of new pollutants such as bisphenol A, APs and the like in the environment are usually low in content, complex in components and more in interfering substances, so that the development of the phenol derivatization reagent which has high sensitivity, high selectivity and good stability, can reach the reaction end point quickly and has no damage to the chromatographic column by-products becomes a key scheme for solving the problems.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
The invention also aims to provide an acyl imidazole compound for detecting phenolic pollutants, which is easy to react with the phenolic compounds, can be used as a derivatization reagent for detecting the phenolic pollutants, and has the advantages of good stability, high reaction sensitivity, small matrix interference, low detection limit, short analysis time, rapid detection and accurate quantification.
It is still another object of the present invention to provide a method for preparing an acyl imidazole compound for detection of phenolic contaminants, which successfully synthesizes a novel compound useful for phenolic contaminants in soil, water, and atmospheric environment by one-step reaction, starting from known available raw materials.
Still another object of the present invention is to provide the use of an acylimidazole compound for the detection of phenolic contaminants as a phenol derivatizing agent in the detection of phenolic contaminants in soil, water, and atmospheric environments.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided an acylimidazole compound for use in detection of phenolic contaminants, having the structure of the following formula (I):
（I）
wherein R is 1 、R 2 、R 3 、R 4 H, CF independently 3 、 NO 2 F, cl or Br.
Preferably, wherein R 2 Is CF (CF) 3 ，R 1 、R 3 、R 4 All are H.
Preferably, wherein R 2 Is NO 2 ，R 1 、R 3 、R 4 All are H.
The invention can be further realized by a preparation method of the acyl imidazole compound for detecting phenolic pollutants, which takes the compound shown as the following formula (II) as raw material, and the raw material is dissolved in an organic solvent and then mixed withN,NPurifying the' -carbonyl diimidazole after one-step reaction to obtain a compound shown in a formula (I);
（II）。
preferably, wherein the compound of formula (II) is mixed withN,NThe molar ratio of the' -carbonyl diimidazole is 1:1-1:1.2.
Preferably, the reaction temperature is room temperature and the reaction time is 1 to 3 h.
Preferably, wherein all organic solvents are tetrahydrofuran.
Preferably, the purification specifically comprises: removing the organic solvent by decompression and spin-drying, mixing neutral alumina with sample, separating and purifying by silica gel column chromatography, wherein the eluent used by the column chromatography is petroleum ether and ethyl acetate with the volume ratio of 5:1.
The object of the present invention can be further achieved by the use of an acylimidazole compound as a phenol derivatizing reagent for the detection of phenol contaminants.
The invention at least comprises the following beneficial effects:
1. the acyl imidazole compound for detecting phenolic pollutants optimizes the substitution position and the number of substituents of the strong electron withdrawing group by adjusting the substituent induction effect on the aromatic ring parent nucleus skeleton, and preferably optimizes the CF at the 2 position 3 The substitution is that the stability of the compound is good, the introduction of the nitro can reduce the stability of the derivative reagent to a certain extent, and the novel acyl imidazole active compound with the stability obviously superior to that of the derivative reagent such as acyl chloride, anhydride, benzyl bromide and the like is synthesized.
2. According to the acyl imidazole compound for detecting phenolic pollutants, provided by the invention, on the premise of keeping the stability of the acyl imidazole compound, different types and numbers of strong electron-withdrawing groups are introduced into molecules, so that the reaction sensitivity of a derivative reagent to a substrate sample is improved to the greatest extent, the preparation method for greatly improving the mass spectrum response efficiency is easy to obtain reaction raw materials, the synthesis condition is simple, the preparation yield is high, and the obtained product is easy to ionize.
3. The acyl imidazole compound for detecting the phenolic pollutants is used as a by-product of the derivatization reaction of the phenolic derivatization reagent and the phenolic compound, the micromolecule has no influence on the chromatographic column, the common problem in the prior art is greatly improved, and the service life of the chromatographic column is better protected. The byproducts of the previous acylation, alkylation, bromination and other derivatization reactions are strong acids such as hydrogen chloride, hydrogen bromide, methanesulfonic acid and the like, and the damage degree to the chromatographic column is large.
4. The acyl imidazole compound for detecting the phenolic pollutants can serve as a phenol derivatization reagent to react with phenol to generate imidazole which can serve as alkali, further catalyze forward progress of the derivatization reaction, and powerfully improve reaction conversion rate.
5. Because the acyl imidazole compound for detecting the phenolic pollutants is used as the phenol derivatization reagent to react with phenol to generate imidazole, exogenous alkali is not required to be added, or only catalytic amount of alkali is required to be added, so that the reaction can be promoted to reach the end point rapidly, and the accurate quantification of phenolic substances is realized.
6. The acyl imidazole compound for detecting the phenolic pollutants is used as a phenolic derivatization reagent to carry out GC-MS detection on an actual sample, and the detection method has the advantages of good stability of the derivatization reagent, high reaction sensitivity, small matrix interference, low detection limit, short analysis time, and capability of rapidly reaching a detection endpoint and accurately quantifying.
7. The preparation method of the acyl imidazole compound for detecting the phenolic pollutants starts from known available raw materials, and the novel compound of the phenolic pollutants in soil, water and atmospheric environment, which can be used for detecting the GC-MS/MS, is obtained through one-step synthesis.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a compound BTFBZI in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the compound BTFBZI in example 1 of the present invention;
FIG. 3 is a chart showing the hydrogen nuclear magnetic resonance spectrum of pNTFBZI as a compound in example 2 of the present invention;
FIG. 4 is a chart showing the nuclear magnetic resonance of pNTFBZI as a compound in example 2 of the present invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of compound 1 in example 3 of the present invention;
FIG. 6 is a nuclear magnetic resonance carbon spectrum of compound 1 in example 3 of the present invention;
FIG. 7 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 2 in example 4 of the present invention;
FIG. 8 is a chart showing the nuclear magnetic resonance carbon spectrum of compound 2 in example 4 of the present invention;
FIG. 9 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 3 in example 4 of the present invention;
FIG. 10 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 3 in example 4 of the present invention;
FIG. 11 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 4 in example 5 of the present invention;
FIG. 12 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 4 in example 5 of the present invention;
FIG. 13 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 5 in example 6 of the present invention;
FIG. 14 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 5 in example 6 of the present invention;
FIG. 15 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 6 in example 6 of the present invention;
FIG. 16 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 6 in example 6 of the present invention;
FIG. 17 is a chart showing the hydrogen nuclear magnetic resonance spectrum of compound 7 in example 7 of the present invention;
FIG. 18 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 7 in example 7 of the present invention;
FIG. 19 is a graph showing the total ion flow of the BTFBZI and phenol-BTFBZI products of example 9 of the present invention;
FIG. 20 is a graph showing the total ion flow of the BTFBZI and bisphenol A-BTFBZI products of example 9 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The experimental methods described in the following embodiments are conventional methods unless otherwise indicated, and the reagents and materials are commercially available.
Example 1 ]
An acylimidazole compound (2, 4-bis (trifluoromethyl) -phenyl) (1H-imidazolyl) methanone (BTFBZI) for use in the detection of phenolic contaminants has the structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
2, 4-Ditrifluoromethylbenzoic acid (517 mg,2.0 mmol) was dissolved in tetrahydrofuran (15 mL) under ice-bath conditions and added dropwiseN,NA solution of' -carbonyldiimidazole CDI (341 mg,2.1 mmol) in tetrahydrofuran (5 mL) was added, and after completion of the addition, the reaction was allowed to warm to room temperature for reaction, and after 1.0 h, the starting material was completely consumed as monitored by TLC. After stopping the reaction, the solvent was removed by spin-on, and neutral alumina was separated by column chromatography (petroleum ether/ethyl acetate 5/1) to give the product as a white solid (540, mg, 87.7% yield). MS (M/z,%) 308 (M + , 100); 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.33 (m, 2H), 8.19 (m, 2H), 7.71 (s, 1H), 7.19 (s, 1H). 13 C 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.
The nuclear magnetic resonance hydrogen spectrum of the compound BTFBZI is shown in figure 1, and the nuclear magnetic resonance carbon spectrum is shown in figure 2.
Example 2 ]
An acylimidazole compound (1H-imidazolyl) (4-nitro-2-trifluoromethyl-phenyl) methanone (pnfbzi) for use in the detection of phenolic contaminants, having the structural formula:
the specific synthetic route is as follows:
the procedure was followed in example 1 to give the product as a white solid (91.2% yield). MS (M/z,%) 285 (M + , 100); 1 H 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). 13 C 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.
The nuclear magnetic resonance hydrogen spectrum of the compound pNTFBZI is shown in figure 3, and the nuclear magnetic resonance carbon spectrum is shown in figure 4.
Example 3 ]
The compound BTFBZI of example 1 was reacted with phenol to synthesize the derivative product.
The derivative product obtained by the reaction with phenol has the following structure:
the specific synthetic route is as follows:
the synthesis steps are as follows:
the compound BTFBZI (155 mg,0.5 mmol) was dissolved in tetrahydrofuran (10 mL), phenol (70 mg,0.75 mmol) and triethylamine (5 mg,0.05 mmol) were added, reacted at room temperature, monitored by TLC, and the starting material was completely consumed within 5 min. After stopping the reaction, the solvent was removed by spin-on chromatography (petroleum ether/ethyl acetate 10/1) to give 3 as a white solid (142, mg, 85.0% yield). MS (M/z,%) 334 (M + , 100); 1 H 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). 13 C NMR (75 MHz, DMSO-d 6 ) Delta 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. The nmr hydrogen spectrum of compound 1 is shown in fig. 5, and the nmr carbon spectrum is shown in fig. 6.
Example 4 ]
The compound BTFBZI of example 1 was reacted with bisphenol a to synthesize the derivative product.
The derivative product obtained by the reaction with bisphenol A has the following structure:
and
the specific synthetic route is as follows:
the synthesis steps are as follows:
compound BTFBZI (770 mg,2.5 mmol) was dissolved in tetrahydrofuran (10 mL), bisphenol A (228 mg,1 mmol) and triethylamine (5 mg,0.05 mmol) were added and reacted at room temperature, monitored by TLC and the starting material was completely consumed within 10 min. After stopping the reaction, the solvent was removed by spin-on chromatography (petroleum ether/ethyl acetate 15/1-5/1) to give compound 2 (bisphenol ester, white solid 572 mg, 80.8%) and compound 3 (monophenol ester, white solid 16 mg, 16.9% yield). Compound 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.
Compound 3: MS (M/z,%) + , 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 = 8.5 Hz, 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.
The nuclear magnetic resonance hydrogen spectrum of the compound 2 is shown in fig. 7, and the nuclear magnetic resonance carbon spectrum is shown in fig. 8. The nuclear magnetic resonance hydrogen spectrum of the compound 3 is shown in fig. 9, and the nuclear magnetic resonance carbon spectrum is shown in fig. 10.
Example 5 ]
The compound pnfbzi of example 2 was reacted with phenol to synthesize the derivative product.
The derivative product obtained by the reaction with phenol has the following structure:
the specific synthetic route is as follows:
the synthesis procedure is as in example 3 to give compound 4.MS (M/z,%): 311 (M + , 100); 1H NMR (300 MHz, 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, 7.5 Hz, 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.
The nuclear magnetic resonance hydrogen spectrum of the compound 4 is shown in fig. 11, and the nuclear magnetic resonance carbon spectrum is shown in fig. 12.
Example 6 ]
The compound pnfbzi of example 2 was reacted with bisphenol a to synthesize the derivative product.
The derivative product obtained by the reaction with bisphenol A has the following structure:
and
the specific synthetic route is as follows:
the synthesis procedure was the same as in example 4 to obtain bisphenol ester compound 5 and monophenol ester compound 6.
Compound 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 = 8.6 Hz, 4H), 7.26 (d, J = 8.5 Hz, 4H), 1.71 (s, 6H). 13CNMR (75 MHz, DMSO-d 6 ) δ 163.95, 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.
The nuclear magnetic resonance hydrogen spectrum of the compound 5 is shown in fig. 13, and the nuclear magnetic resonance carbon spectrum is shown in fig. 14.
Compound 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.
The nuclear magnetic resonance hydrogen spectrum of the compound 6 is shown in fig. 15, and the nuclear magnetic resonance carbon spectrum is shown in fig. 16.
Example 7 ]
The synthesis of the derivative 7 was carried out in the same manner as in example 3 (note: the compound oNTFBZI which was present in a stable state was not obtained in the isolation process). Compound 7 MS (M/z,%) 311 (M + , 100); 1 H 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.
The nuclear magnetic resonance hydrogen spectrum of the compound 7 is shown in figure 17, and the nuclear magnetic resonance carbon spectrum is shown in figure 18.
Derivative product formation mechanism:
the formation mechanism of the phenol derivative product comprises the following three steps:
（1）N,Nnucleophilic addition elimination reaction is carried out on' -carbonyl diimidazole and carboxylic acid, and side product imidazole is removed;
(2) Imidazole serves as a base catalysis function, further nucleophilic attack on an anhydride intermediate, leaving imidazole of another molecule, and simultaneously removing one molecule of carbon dioxide to obtain an acyl imidazole stable intermediate;
(3) The phenolic hydroxyl of the phenolic compound nucleophilic attacks the carbonyl of the acyl imidazole intermediate, and imidazole small molecules are removed to obtain phenolic ester derivatives, so that the reaction end point is reached.
Example 8 ]
Stability evaluation of acyl imidazoles for phenolic contaminant detection.
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As a result of analyzing the stability of the three phenol derivative reagents, it was found that the stability of the compounds pNTFBZI and oNTFBZI is reduced after the introduction of the aromatic ring, wherein the compound oNTFBZI cannot exist stably in the separation process and is easy to decompose; the stability of the compound pNTFBZI is relatively good, which shows that the stability of the derivative reagent is relatively less affected when the nitro group is in the para position of the acyl imidazole. TLC continuous monitoring found that compound pnfbzi was stable over 72 hours, while crystals of compound BTFBZI were stable over 6 weeks (continuous monitoring by thin layer chromatography, developing solvent petroleum ether/ethyl acetate=2/1), and thus compound BTFBZI was suitable for development as a highly selective, highly sensitive, stable phenolic derivatizing reagent.
Example 9 ]
The compound BTFBZI detects phenol and bisphenol a in water:
1. phenol-BTFBZI, bisphenol a-BTFBZI standard solution:
1.1 BTFBZI derived solutionsρ=500. Preparation of μg/mL:
5 mg of BTFBZI was added to methylene chloride and the volume was adjusted to 10 mL to prepare a 500. Mu.g/mL solution derived from BTFBZI.
1.2, preparing phenol-BTFBZI standard solution:
100, 200, 500, 1000, 2000 and 5000. Mu.g/L of phenol standard solution of 1.1 mL are respectively taken, 20. Mu.L of triethylamine and 100. Mu.L of 500. Mu.g/mL of BTFBZI solution are added, and the mixture is left to stand for 3h at normal temperature to prepare a phenol-BTFBZI standard solution.
1.3, preparation of bisphenol A-BTFBZI standard solution:
100, 200, 500, 1000, 2000 and 5000. Mu.g/L bisphenol A standard solution of 1mL are respectively taken, 20. Mu.L triethylamine and 100. Mu.L 500. Mu.g/mL BTFBZI solution are added, and the mixture is left to stand for 3h at normal temperature to prepare bisphenol A-BTFBZI standard solution.
2. BTFBZI detects phenol in water, bisphenol a pretreatment:
to a 200 mL water sample was added 20 mL dichloromethane-ethyl acetate (V/v=1:1), and after shaking for 3min, it was allowed to stand until the aqueous and organic phases were sufficiently separated, the organic phase was collected and dehydrated over anhydrous sodium sulfate. Repeating the extraction steps for 2 times, concentrating to 1mL by rotary evaporation and nitrogen blowing, adding 20 mu L of triethylamine and 100 mu L of 500 mu g/mL of BTFBZI derivative solution, standing for 3 hours at normal temperature, and measuring.
3. Instrument conditions:
gas chromatography conditions:
sample inlet: 290 ℃; split ratio: 10:1 column flow: 1.2 mL/min;
heating program: 35 ℃ (4 min), 40 ℃/min rise to 170 ℃,15 ℃/min rise to 310 ℃ (3 min);
chromatographic column: DB-5MS 30 m x 0.25 mm x 0.25 μm;
mass spectrometry conditions:
transmission line temperature: 290 ℃; ion source temperature: 230 ℃; quadrupole temperature: 150 ℃;
ion source electron energy: 70eV; the data acquisition mode is as follows: SCAN (m/z: 50-600).
4. Retention time of target compound, quantitative ion, linear equation and correlation coefficient: see table 1:
TABLE 1 retention time of standard solutions, quantitative ion, auxiliary ion and linear equation
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The total ion flow diagram of the BTFBZI and phenol-BTFBZI products is shown in FIG. 19; the total ion flow spectra of the BTFBZI and bisphenol A-BTFBZI products are shown in FIG. 20.
Comparative example 1 ]
Pentafluorobenzyl bromide is a derivatization reagent commonly used for detecting phenolic compounds in environmental samples, and is used for derivatization of the phenolic compounds in both a gas chromatography-mass spectrometry method for detecting water quality phenolic compounds (HJ 744-2015) and a gas chromatography-mass spectrometry method for detecting soil and sediment semi-volatile organic compounds (HJ 834-2017), and the derivatization products are detected through the gas chromatography-mass spectrometry to achieve the aim of quantitative analysis of the phenolic target substances. The traditional derivatization reagent pentafluorobenzyl bromide belongs to the technical field of tear-gas substances, has high toxicity, and is extremely unfriendly to gas chromatographic columns because an inorganic salt catalyst (potassium carbonate) is required to be added in the derivatization process. Although the gas chromatography mass spectrometry has the advantages of accurate quantification and good reproducibility, the method is only suitable for detecting the phenol compounds with relatively high concentration in environmental samples because of the lower sensitivity of the traditional derivative products; meanwhile, the traditional method has poor recovery rate and low accuracy; in addition, the phenolic compounds in the environmental samples are determined by using a pentafluorobenzyl bromide derivative-gas chromatography mass spectrometry method, so that the pretreatment is complicated, more prepared pretreatment solutions are needed, the reaction has high temperature requirements, and the efficient detection of low-concentration samples is not facilitated.
The comparative data of the derivatization reagent compound pentafluorobenzyl bromide used for detecting phenolic compounds in environmental samples and the BTFBZI compound of the invention used for detecting phenolic compounds in the prior art are shown in table 2 below.
TABLE 2 comparison of Pentafluorobenzyl bromide with BTFBZI for detection of phenolic Compounds
Derivatizing agent BTFBZI Pentafluorobenzyl bromide
Physicochemical Properties White and odorless. Tear promoting substances have great harm to the body of experimental staff.
Detection method GCMS GCMS
Detection limit (μg/L) 0.02 0.1（HJ744-2015）
Derivatization temperature Normal temperature 60°C
Derivatization conditions 1mL sample was added with 20. Mu.L of triethylamine, 100. Mu.L of 500 mu.g/mL of BTFBZI solution was reacted at room temperature for 3 h. 100. Mu.L of pentafluorobenzyl bromide and 0.1 g/mL of potassium carbonate solution were added to the 8 mL sample, derivatization at 60 ℃ for 60 min, replacing the solvent system to n-hexane, and concentrating to constant volume to 1mL.
Recovery rate 95.7%~99.4% 82.5%~87.5
As can be seen from the above Table 2, in the prior art, the pentafluorobenzyl bromide used for detecting the phenolic compounds in the environmental samples has high toxicity of the derivative products, and the inorganic salt catalyst is not friendly to chromatographic columns in the derivative process, and is generally detected by adopting a gas chromatography-mass spectrometry method. Although the gas chromatography mass spectrometry has the advantages of accurate quantification and good reproducibility, the method is only suitable for detecting the phenol compounds with relatively high concentration in the soil sample due to lower sensitivity; and poor recovery. The BTFBZI compound provided by the invention is used as a derivatization reagent for GC-MS detection of a detection sample, and has the advantages of good derivatization reagent stability, high mass spectrum response, small matrix interference, low detection limit, good reproducibility, short analysis time, capability of rapidly reaching a detection endpoint, accuracy and quantification and high recovery rate.
Although embodiments of the invention have been disclosed above, they are not limited to the use listed in the specification and embodiments. It can be applied to various fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. Therefore, the invention is not to be limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.

Claims (7)

1. An acylimidazole compound for use in the detection of phenolic contaminants having the structure of formula (I):
（I）
wherein R is 2 Is CF (CF) 3 Or NO 2 ，R 1 、R 3 、R 4 All are H.
2. A method for preparing the acyl imidazole compound for detecting phenolic pollutants according to claim 1, which takes the compound shown in the following formula (II) as a raw material, and the raw material is dissolved in an organic solvent and then mixed withN, NPurifying the' -carbonyl diimidazole after one-step reaction to obtain a compound shown in a formula (I);
（II）；
wherein R is 2 Is CF (CF) 3 Or NO 2 ，R 1 、R 3 、R 4 All are H.
3. The method of claim 2, wherein the compound of formula (II) is mixed withN, NThe molar ratio of the' -carbonyl diimidazole is 1:1-1:1.2.
4. The method of claim 2, wherein the reaction temperature is room temperature and the reaction time is 1 to 3 h.
5. The method of claim 2, wherein the organic solvent is tetrahydrofuran.
6. The method according to claim 2, wherein purifying specifically comprises: removing the organic solvent by decompression and spin-drying, mixing neutral alumina with sample, separating and purifying by silica gel column chromatography, wherein the eluent used by the column chromatography is petroleum ether and ethyl acetate with the volume ratio of 5:1.
7. Use of an acylimidazole compound for use in the detection of a phenolic contaminant according to claim 1 as a phenolic derivatizing reagent.
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