CN117304029A - 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester, one-pot synthesis preparation method and application thereof - Google Patents
4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester, one-pot synthesis preparation method and application thereof Download PDFInfo
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- 229960002944 cyclofenil Drugs 0.000 title claims abstract description 86
- -1 cyclophenyl diester Chemical class 0.000 title claims abstract description 48
- GVOUFPWUYJWQSK-UHFFFAOYSA-N Cyclofenil Chemical group C1=CC(OC(=O)C)=CC=C1C(C=1C=CC(OC(C)=O)=CC=1)=C1CCCCC1 GVOUFPWUYJWQSK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000005690 diesters Chemical class 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- PQCXFUXRTRESBD-UHFFFAOYSA-N (4-methoxycarbonylphenyl)boronic acid Chemical compound COC(=O)C1=CC=C(B(O)O)C=C1 PQCXFUXRTRESBD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- PUYOAVGNCWPANW-UHFFFAOYSA-N 2-methylpropyl 4-aminobenzoate Chemical compound CC(C)COC(=O)C1=CC=C(N)C=C1 PUYOAVGNCWPANW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001917 fluorescence detection Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/76—Ring systems containing bridged rings containing three rings containing at least one ring with more than six ring members
- C07C2603/84—Ring systems containing bridged rings containing three rings containing at least one ring with more than six ring members containing rings with more than eight members
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
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Abstract
The invention relates to 4,16- [2.2] ring-imitated phenyl diester and 4- [2.2] ring-imitated phenyl monoester, a one-pot synthesis preparation method and application thereof; the preparation method comprises the steps of adding 4, 16-dibromo [2.2] cyclobenzene, 4-methoxycarbonyl phenylboronic acid, carbonate and palladium catalysts into a solvent, adding 2-3 drops of water, mixing, isolating air, and carrying out Suzuki coupling reaction to obtain a mixture liquid of 4,16- [2.2] cyclobenzene diester and 4- [2.2] cyclobenzene monoester; and carrying out suction filtration, extraction, drying and separation purification on the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester mixed solution to respectively obtain 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester, wherein the obtained 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester can be used as fluorescent agents.
Description
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester, a one-pot synthesis preparation method thereof, application in the field of fluorescent sensing and application of the 4,16- [2.2] cyclophenyl diester in fluorescent quantitative identification of o-dichlorobenzene.
Background
Among chlorobenzene compounds, o-dichlorobenzene has strong odor, is easy to stimulate skin, eyes and respiratory airways of human body, has accumulation effect in human body, inhibits nerve centers, and damages liver and kidney in severe cases. Therefore, quantitative detection of trace o-dichlorobenzene in the environment, particularly in water, is an important content in pollutant detection. However, the current detection methods include gas chromatography, liquid chromatography and mass spectrometry, which are generally expensive, complicated in conditions and difficult to operate. The fluorescence detection method is widely focused and researched by more researchers with the advantages of convenience, high efficiency, low cost, real-time detection and the like.
At present, the o-dichlorobenzene fluorescent detection agent is less, the synthesis process of the common fluorescent probe compound is complex, the cost is high, and the method is difficult to widely apply. [2.2] the cyclic analog compound is used as an important fluorescent material to construct a framework, and has little application (Tetrahedron Lett.,2017,58,271;Dyes and Pigments,2022,205,110491) in fluorescent sensing, and particularly has blank application in fluorescent identification of o-dichlorobenzene.
Therefore, the invention aims at the problems, and the invention provides a 4,16- [2.2] cyclophenyl diester and a 4- [2.2] cyclophenyl monoester, a one-pot synthesis preparation method thereof, application in the field of fluorescence sensing and application of the 4,16- [2.2] cyclophenyl diester in fluorescence quantitative identification of o-dichlorobenzene.
Disclosure of Invention
The invention aims to provide 4,16- [2.2] cyclobenzene-like diester and 4- [2.2] cyclobenzene-like monoester, a one-pot synthesis preparation method and application thereof, and the technical problems that in the prior art, fluorescent detection aiming at o-dichlorobenzene is less, the synthesis process is complex, the cost is high and the fluorescent method cannot be popularized to detect the o-dichlorobenzene are solved by the preparation method of the 4,16- [2.2] cyclobenzene-like diester and the 4- [2.2] cyclobenzene-like monoester.
The invention provides a preparation method for synthesizing 4,16- [2.2] cyclobenzene diester and 4- [2.2] cyclobenzene monoester by one pot, which is characterized by comprising the following steps: the method comprises the following steps:
adding 4, 16-dibromo [2.2] cyclobenzene, 4-methoxycarbonyl phenylboronic acid, carbonate and palladium catalyst into a solvent, adding 2-3 drops of water, mixing, isolating air and carrying out Suzuki coupling reaction to obtain a mixture solution of 4,16- [2.2] cyclobenzene diester and 4- [2.2] cyclobenzene monoester;
and carrying out suction filtration, extraction, drying and separation purification on the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester mixed solution to obtain the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester respectively.
Preferably, the molar ratio of 4, 16-dibromo [2.2] cycloform to 4-methoxycarbonylphenylboronic acid is 1:3.
preferably, the molar ratio of 4, 16-dibromo [2.2] cycloimitation to palladium catalyst is 100:1.
Preferably, the palladium-based catalyst is tetrakis (triphenylphosphine) palladium; the solvent is tetrahydrofuran or dioxane; the carbonate is potassium carbonate or sodium carbonate.
Preferably, the reaction temperature in the Suzuki coupling reaction process is 70-90 ℃; when in Suzuki coupling reaction, oxygen is isolated for reaction, and the Suzuki coupling reaction time is 24-36h under the protection of nitrogen.
Preferably, in the extraction process, dichloromethane or chloroform is used as the extraction liquid.
Preferably, in the extraction, separation and purification process, silica gel column chromatography is adopted for separation, and petroleum ether/dichloromethane with the volume ratio of 1:1 is adopted as a separating agent.
The invention also provides a 4,16- [2.2] cyclophenyl diester and a 4- [2.2] cyclophenyl monoester obtained based on the preparation method of the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester synthesized by one pot according to any one of foolproof farmers,
the structural formula of the 4,16- [2.2] cyclobenzene diester is as follows:
the structural formula of the 4- [2.2] cyclobenzene monoester is as follows:
the invention also provides an application of the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester in the fluorescence sensing field.
The invention also provides an application of the 4,16- [2.2] cyclophenyl diester in fluorescent quantitative identification of o-dichlorobenzene based on the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester.
The invention provides a 4,16- [2.2] cyclobenzene-like diester and 4- [2.2] cyclobenzene-like monoester, a one-pot synthesis preparation method thereof, application in the field of fluorescence sensing and application of the 4,16- [2.2] cyclobenzene-like diester in fluorescence quantitative identification of o-dichlorobenzene, which have the following progress compared with the prior art:
1. the preparation method for synthesizing the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester by one pot provided by the invention has the advantages of simple synthesis method, easiness in preparation, convenience in purification, higher yield and good stability, and the obtained 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester have fluorescence emission performance and fluorescence performance.
2. The preparation method for synthesizing the 4,16- [2.2] cyclobenzene-like diester and the 4- [2.2] cyclobenzene-like monoester in one pot provided by the invention can be used for carrying out fluorescent quantitative detection on o-dichlorobenzene, and has potential application prospects in the aspect of environment detection.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 4,16- [2.2] cyclobenzene diester as described in example one;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a 4- [2.2] cyclobenzene monoester as described in example one;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of 4,16- [2.2] cyclophenyl-simulated diester as described in example one;
FIG. 4 is a nuclear magnetic resonance carbon spectrum of a 4- [2.2] cyclobenzene monoester as described in example one;
FIG. 5 is a spectrum of 4,16- [2.2] cyclobenzene-like diester aggregation-induced enhanced fluorescence as described in example one
FIG. 6 is an aggregation-induced enhanced fluorescence spectrum of 4- [2.2] cyclophenyl monoester as described in example one;
FIG. 7 is a fluorescence spectrum of 4,16- [2.2] cyclobenzene-like diester used for fluorescent quantitative identification of trace amounts of o-dichlorobenzene in water as described in example one;
FIG. 8 is a graph showing the sum of detection limits of the fluorescent quantitative identification of trace amounts of o-dichlorobenzene in water using 4,16- [2.2] cyclophenyl diester as described in example one.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method for synthesizing 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester by one pot, which comprises the following steps:
adding 4, 16-dibromo [2.2] cyclobenzene, 4-methoxycarbonyl phenylboronic acid, carbonate and palladium catalyst into a solvent, adding 2-3 drops of water, mixing, isolating air and carrying out Suzuki coupling reaction to obtain a mixture solution of 4,16- [2.2] cyclobenzene diester and 4- [2.2] cyclobenzene monoester;
and carrying out suction filtration, extraction, drying and separation purification on the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester mixed solution to obtain the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester respectively.
Specifically, the molar ratio of 4, 16-dibromo [2.2] cycloform to 4-methoxycarbonylphenylboronic acid is 1:3.
specifically, the molar ratio of the 4, 16-dibromo [2.2] cycloimitation to the palladium catalyst is 100:1.
Specifically, the palladium catalyst is tetra (triphenylphosphine) palladium; the solvent is tetrahydrofuran or dioxane; the carbonate is potassium carbonate or sodium carbonate.
Specifically, the reaction temperature in the Suzuki coupling reaction process is 70-90 ℃; when in Suzuki coupling reaction, oxygen is isolated for reaction, and the Suzuki coupling reaction time is 24-36h under the protection of nitrogen.
Specifically, in the extraction process, dichloromethane or chloroform is adopted as an extraction liquid.
Specifically, in the extraction, separation and purification process, silica gel column chromatography is adopted for separation, and petroleum ether/dichloromethane with the volume ratio of 1:1 is adopted as a separating agent.
The invention also provides a 4,16- [2.2] cyclophenyl diester and a 4- [2.2] cyclophenyl monoester obtained based on the preparation method of the one-pot synthesis of the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester, which is characterized in that:
wherein, the structural formula of the 4,16- [2.2] cyclobenzene diester is as follows:
the structural formula of the 4- [2.2] cyclobenzene monoester is as follows:
the invention also provides an application of the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester in the fluorescence sensing field.
The invention also provides an application of the 4,16- [2.2] cyclophenyl diester in fluorescent quantitative identification of o-dichlorobenzene based on the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester.
Example 1
A preparation method for synthesizing a mixture of 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester in one pot comprises the following steps:
101 1g of 4, 16-dibromo [2.2]]Cycloform (2.75 mmol), 1.49g of 4-methoxycarbonylphenylboronic acid (8.25 mmol), 2.27g of potassium carbonate (16.5 mmol), 32mg of tetrakis (triphenylphosphine) palladium (2.75X10 -3 mmol) was added to 5.0mL of tetrahydrofuran, and 2-3 drops (added dropwise with a pipette) were added, and the Suzuki coupling reaction was carried out at 80℃under nitrogen, after 24 hours, a solution containing 4,16- [2.2]Cyclic phenyl diester and 4- [2.2]]A mixture of cyclic phenyl monoesters;
102 Cooling the mixed solution containing 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester to room temperature, and then extracting, drying and purifying to obtain the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester respectively.
Specifically, the synthetic route of this embodiment is:
in the extraction process, adding water (10.0 mL) into the mixed solution, extracting with 10mL of dichloromethane for three times to obtain an extraction mixed solution, removing the solvent from the extraction mixed solution by using a rotary evaporation device, and drying the extraction mixed solution by using a vacuum drying box to obtain a mixture to be separated and purified;
the mixture to be separated and purified was purified by column chromatography on silica gel using a developing solvent of petroleum ether/methylene chloride in a volume ratio of 1:1 to give pure product 1 (0.37 g,57% yield) and pure product 2 (0.101 g,21% yield).
As shown in fig. 1, the nuclear magnetic resonance hydrogen spectrum of pure product 1 was 1H NMR (400 mhz, cdcl 3) δ8.17 (d, j=8.1 hz, 4H), 7.60 (d, j=8.1 hz, 4H), 6.70 (d, j=5.5 hz, 4H), 6.59 (d, j=7.7 hz, 2H), 3.98 (s, 6H), 3.43 (s, 2H), 3.07 (s, 2H), 2.87 (d, j=9.8 hz, 2H), 2.76 (s, 2H).
As shown in fig. 2, the nuclear magnetic resonance hydrogen spectrum of pure product 2 is 1H NMR (400 mhz, cdcl 3) delta 8.14 (d, j=8.1 hz, 2H), 7.55 (d, j=8.3 hz, 2H), 6.68-6.51 (m, 7H), 3.96 (d, j=0.7 hz, 3H), 3.39 (ddd, j=12.6, 10.0,2.9hz, 1H), 3.22-3.10 (m, 3H), 3.09-3.00 (m, 1H), 3.00-2.83 (m, 2H), 2.66-2.58 (m, 1H).
As shown in fig. 3, the nmr carbon spectrum of pure product 1: 13C NMR (126 MHz, CDCl 3) delta 167.1,145.7,141.1,140.0,137.1,134.9,132.3,129.9,129.8,129.7,128.6,52.2,34.7,33.8.
As shown in fig. 4, the nmr carbon spectrum of pure product 2: 13C NMR (126 MHz, CDCl 3) delta 167.1,145.8,140.7,139.9,139.6,139.4,137.2,136.0,133.2,132.8,132.6,132.1,132.0,129.8,129.7,129.6,128.4,52.1,35.5,35.2,34.9,34.1.
The structural formula of the pure product 1 thus obtained is:
the structural formula of the obtained pure substance 2 is
Fluorescence spectrum experiment of pure 1 and pure 2
Pure 1 and pure 2 were dissolved in tetrahydrofuran solution to give a concentration of 5X 10 -3 First concentrated liquid of mol/L and 5X 10 -3 And mol/L of second concentrated liquid storage.
2970 μl of each of two sets of tetrahydrofuran solutions having water contents (v/v) of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90% was prepared, and 30 μl of each of the first concentrated solution and the second concentrated solution was added to each of the two sets of tetrahydrofuran solutions having water contents (v/v) of 0%, 10%, 20%, 30%, 50%, 60%, 80%, and 90%, to obtain a first mixed solution having water contents (v/v) of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%, and a second mixed solution having water contents (v/v) of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%, and fluorescence spectrum signals were measured using a fluorescence spectrometer under the following measurement conditions: the excitation wavelength was 288nm, the slit widths were 5nm, and the voltage was 450 v.
As shown in fig. 5, in the first mixed solution, the fluorescence signal intensity increased when the water content increased from 0% to 70%, and the fluorescence signal intensity decreased when the water content increased from 70% to 80%.
As shown in fig. 6, in the second mixed solution, the fluorescence signal intensity increases when the water content increases from 0% to 40%, and decreases when the water content increases from 40% to 80%.
The obtained 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester have aggregation-induced fluorescence enhancement performance.
Fluorescence spectrum detection experiment of pure 1-o-dichlorobenzene
Dissolving pure substance 1 in tetrahydrofuran solution to obtain a concentration of 1×10 -3 A concentrated stock solution of mol/L;
THF-H having 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% o-dichlorobenzene content (v/v) and 70% water content was prepared 2 O solutions 2967, 2964, 2961, 2958, 2955, 2952, 2949 and 2946. Mu.L, and were added to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% of THF-H having a water content of 70%, respectively 2 30. Mu.L of the solution of O was added to a concentration of 1X 10 -3 The concentrated stock solution of mol/L, and THF-H with water content of 70% and 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% and 0.8% of o-dichlorobenzene content (v/v) is obtained 2 An O mixed solution;
THF-H having a water content of 70% and an ortho-dichlorobenzene content (v/v) of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% by means of a fluorescence spectrometer 2 And (3) carrying out fluorescence spectrum signal testing on the O mixed solution, wherein the measurement conditions of spectrum data are as follows: the excitation wavelength was 288nm, the slit widths were 5nm, and the voltage was 450 v.
As shown in FIG. 7, the fluorescence detection intensity in the THF-H2O mixed solution gradually decreased with the increase of the content of O-dichlorobenzene, indicating that pure 1 was capable of fluorescence detection of O-dichlorobenzene in the aqueous solution.
The content of the O-dichlorobenzene in the THF-H2O mixed solution in the graph of FIG. 8 has a corresponding linear relation with fluorescence detection intensity, the detection limit of the fluorescent quantitative detection of trace O-dichlorobenzene in the THF-H2O mixed solution is 5.11ppm, and the detection limit of the mesoporous molecular sieve material MCM-41 reported at present is 13.0+/-0.65 pM (Colloids and Surfaces A,2019,562,161).
The preparation method for synthesizing the 4,16- [2.2] cyclophenyl diester and the 4- [2.2] cyclophenyl monoester by one pot provided by the invention has the advantages of simple synthesis method, easiness in preparation, convenience in purification, higher yield and good stability, and the obtained 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester have fluorescence emission performance and fluorescence performance.
The preparation method for synthesizing the 4,16- [2.2] cyclobenzene-like diester and the 4- [2.2] cyclobenzene-like monoester in one pot provided by the invention can be used for carrying out fluorescent quantitative detection on o-dichlorobenzene, and has potential application prospects in the aspect of environment detection.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method for synthesizing 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester in one pot is characterized by comprising the following steps: the method comprises the following steps:
adding 4, 16-dibromo [2.2] cyclobenzene, 4-methoxycarbonyl phenylboronic acid, carbonate and palladium catalyst into a solvent, adding 2-3 drops of water, mixing, isolating air and carrying out Suzuki coupling reaction to obtain a mixture solution of 4,16- [2.2] cyclobenzene diester and 4- [2.2] cyclobenzene monoester;
and (3) carrying out suction filtration, extraction, drying, separation and purification on the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester mixed solution to obtain the 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester respectively.
2. The method for preparing the one-pot synthetic 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester according to claim 1, which is characterized in that: the molar ratio of the 4, 16-dibromo [2.2] cycloform to the 4-methoxycarbonyl phenylboronic acid is 1:3.
3. the method for preparing the one-pot synthetic 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester according to claim 1, which is characterized in that: the molar ratio of the 4, 16-dibromo [2.2] cycloimitation to the palladium catalyst is 100:1.
4. The method for preparing the one-pot synthetic 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester according to claim 1, which is characterized in that: the palladium catalyst is tetra (triphenylphosphine) palladium; the solvent is tetrahydrofuran or dioxane; the carbonate is potassium carbonate or sodium carbonate.
5. The method for preparing the one-pot synthetic 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester according to claim 1, which is characterized in that: the reaction temperature in the Suzuki coupling reaction process is 70-90 ℃; when in Suzuki coupling reaction, oxygen is isolated for reaction, and the Suzuki coupling reaction time is 24-36h under the protection of nitrogen.
6. The method for preparing the one-pot synthetic 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester according to claim 1, which is characterized in that: in the extraction process, dichloromethane or chloroform is adopted as the extract liquid.
7. The method for preparing the one-pot synthetic 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester according to claim 1, which is characterized in that: in the extraction, separation and purification process, silica gel column chromatography is adopted for separation, and petroleum ether/dichloromethane with the volume ratio of 1:1 is adopted as a separating agent.
8. A 4,16- [2.2] cyclophenyl diester and a 4- [2.2] cyclophenyl monoester obtained based on the one-pot synthesis of a 4,16- [2.2] cyclophenyl diester and a 4- [2.2] cyclophenyl monoester as claimed in any one of claims 1 to 7, characterized in that: wherein,
the structural formula of the 4,16- [2.2] cyclobenzene diester is as follows:
the structural formula of the 4- [2.2] cyclobenzene monoester is as follows:
9. use of 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester according to claim 8 in the field of fluorescence sensing.
10. Use of 4,16- [2.2] cyclophenyl-like diesters based on 4,16- [2.2] cyclophenyl-like diesters and 4- [2.2] cyclophenyl-like monoesters according to claim 8 for the fluorescent quantitative identification of o-dichlorobenzene.
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