Fluorene derivative fluorescent material, preparation method thereof and application thereof in detection of gas-phase phthalate plasticizer
阅读说明：本技术 芴衍生物类荧光材料及其制备方法和在检测气相邻苯二甲酸酯类塑化剂中的应用 (Fluorene derivative fluorescent material, preparation method thereof and application thereof in detection of gas-phase phthalate plasticizer ) 是由 车延科 邱长坤 于 2019-09-11 设计创作，主要内容包括：本发明提供了一种如式(I)所示的芴衍生物类荧光材料及其制备方法和在检测气相邻苯二甲酸脂类塑化剂中的应用,其荧光量子产率为5-50％。该材料具有的层级聚集体结构具有较大的表面积,增加了与检测气体接触的表面积,因而使检测的灵敏度高(ppb级)。并且该材料可应用于检测实际材料(如保鲜膜等)中是否添加邻苯二甲酸酯类塑化剂。<Image he="294" wi="700" file="DDA0002199693770000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a fluorene derivative fluorescent material shown as a formula (I), a preparation method thereof and application thereof in detection of gas-phase phthalate plasticizers, wherein the fluorescence quantum yield of the fluorene derivative fluorescent material is 5-50%. The material has a hierarchical aggregate structure with a large surface area, which increases the surface area in contact with the detection gas, thus enabling high sensitivity (ppb level) of detection. And the material can be used for detecting whether the phthalate plasticizer is added in the actual material (such as preservative film and the like).)
1. A fluorene derivative represented by the formula (I):
wherein: a. the1、A2Identical or different, independently of one another, from nitro, cyano, nitroalkyl, cyanoalkyl, nitrocycloalkyl, nitroheterocyclyl, cyanocycloalkyl or cyanoheterocyclyl; r1、R2Identical or different, independently of one another, from the group consisting of hydrogen, alkyl, alkyloxy, alkenyl, alkenyloxy, aryl, aryloxy, heteroaryl, heteroaryloxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy; n is an integer of 1 or more, for example, an integer of 1 to 6.
2. Fluorene derivative according to claim 1, wherein a is1、A2Identical or different, independently of one another, from nitro C1-12Alkyl, cyano C1-12Alkyl, nitro C1-12Cycloalkyl, nitro C1-12Heterocyclyl radical, cyano radical C1-12Cycloalkyl or cyano C1-12A heterocyclic group; r1、R2Identical or different, independently of one another, from hydrogen, C1-12A linear or branched alkyl group; n is an integer of 1 to 6.
3. Fluorene derivative according to claim 1 or 2, wherein a is1、A2Identical or different, independently of one another, from nitro C1-6Alkyl or cyano C1-6An alkyl group; r1、R2Identical or different, independently of one another, from C1-8Linear or branched alkyl of (a); n is an integer of 1 to 6.
4. A fluorene derivative according to any one of claims 1 to 3, wherein A is1、A2Are identical or different and are selected independently of one another
R1、R2Are identical or different and are selected independently of one another
Wherein the content of the first and second substances,
5. A fluorescent material formed by self-assembly of the compound according to any one of claims 1 to 4.
6. The method for preparing a fluorescent material according to claim 5, comprising the steps of:
(1) reacting the compound a1 with pivaloyl diboron to obtain a compound a 2;
(2) reacting the compound a2 with the compound a3 to obtain a 4;
(3) reacting the compound a5 with pivaloyl diboron to obtain a compound a 6;
(4) reacting a compound a6 with a compound a4 to obtain a fluorene derivative shown as a formula (I);
(5) dissolving a fluorene derivative shown in a formula (I) in a good solvent, and then adding a poor solvent for self-assembly to obtain the fluorescent material;
wherein R is1、R2、A1、A2N has the definition as described above, wherein m is an integer of 1 to 6.
7. The method according to claim 6, wherein the good solvent is selected from the group consisting of haloalkane solvents; the poor solvent is selected from an alcohol solvent, a ketone solvent or an alkane solvent.
8. The production method according to claim 6 or 7, wherein the good solvent is at least one selected from chloroform and methylene chloride; the poor solvent is selected from at least one of methanol, ethanol, acetone and n-hexane.
9. The production method according to any one of claims 6 to 8, wherein the volume ratio of the good solvent to the poor solvent is from 1:5 to 1: 30.
10. Use of the fluorescent material according to claim 5 for detecting phthalate plasticizers;
the phthalate plasticizer may be one or more of dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBzP), di (2-ethyl) hexyl phthalate (DEHP), di-n-octyl phthalate (DOP), and diisononyl phthalate (DiNP).
Technical Field
The invention belongs to the technical field of fluorescent materials, and particularly relates to a fluorene derivative fluorescent material, a preparation method thereof and application thereof in detection of a gas-phase phthalate plasticizer.
Background
The plasticizer is an external aid which is widely used in industrial production and is used for improving the processing performances of plastic toughness, shaping and the like. In 2010, the worldwide plastic demand reaches 2 hundred million tons, and the total sales of the plasticizer accounts for 60 percent of the plastic additive. Polyvinyl chloride (PVC) has been the most popular plastic produced in the world and is used in a wide variety of applications. The product has wide application in building materials, industrial products, floor leathers, artificial leathers, pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like. Phthalate (PAEs) compounds are the most widely used class of plasticizers added to polyvinyl chloride materials. In 2010, the demand of phthalate plasticizers in China breaks through 100 million tons, and accounts for about 80 percent of the total output of the plasticizers. Phthalate plasticizers are known to be: dimethyl phthalate (DMP); diethyl phthalate (DEP); di-n-butyl phthalate (DBP); butyl benzyl phthalate (BBzP); di (2-ethyl) hexyl phthalate (DEHP); di-n-octyl phthalate (DOP); diisononyl phthalate (DiNP), and the like.
Phthalate plasticizers, which are structurally similar to hormones and can mimic the estrogenic effects, are known as "environmental endocrine disruptors" or "estrogen-like hormones". PAEs can enter human bodies through the ways of respiratory tract, digestive tract, skin and the like, and at present, the research at home and abroad discovers that the pollution condition of the PAEs of people is quite serious, and the PAEs are detected in the blood of premature girls, urine samples of women in childbearing age and breast milk. As an environmental hormone, PAEs are ubiquitous in all aspects of people's daily life, plasticizers exist in air, soil and water, and the influence on human health is mainly determined by the intake amount of PAEs. If a large amount of plasticizer is eaten for a long time, the chronic harm can be brought to the reproductive system, the immune system and the digestive system of a human body.
Because phthalate plasticizers do not have chemical bonds or functions with polymers in polyvinyl chloride, the phthalate plasticizers can be evaporated into the atmospheric environment and further enter the respiratory and digestive systems of people, thereby threatening the environment and personal safety. The methods reported at present for detecting phthalate plasticizers mainly focus on Gas Chromatography (GC), Liquid Chromatography (LC), gas chromatography-mass spectrometry (GC-MS), etc., but these methods are high in cost and complex in instrument operation, and thus are difficult to use on a large scale.
Disclosure of Invention
In order to improve the problems, the invention provides a fluorene derivative, the structure of which is shown as formula (I):
wherein: a. the1、A2Identical or different, independently of one another, from nitro, cyano, nitroalkyl, cyanoalkyl, nitrocycloalkyl, nitroheterocyclyl, cyanocycloalkyl or cyanoheterocyclyl; r1、R2Identical or different, independently of one another, from the group consisting of hydrogen, alkyl, alkyloxy, alkenyl, alkenyloxy, aryl, aryloxy, heteroaryl, heteroaryloxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy; n is an integer of 1 or more, for example, an integer of 1 to 6;
according to an embodiment of the invention, A1、A2Identical or different, independently of one another, from nitro C1-12Alkyl, cyano C1-12Alkyl, nitro C1-12Cycloalkyl, nitro C1-12Heterocyclyl radical, cyano radical C1-12Cycloalkyl or cyano C1-12A heterocyclic group; r1、R2Identical or different, independently of one another, from hydrogen, C1-12A linear or branched alkyl group; n is an integer of 1 to 6;
according to an embodiment of the invention, A1、A2Identical or different, independently of one another, from nitro C1-6Alkyl or cyano C1-6An alkyl group; r1、R2Identical or different, independently of one another, from C1-8Linear or branched alkyl of (a); n is an integer of 1 to 6;
as an example, A1、A2Are identical or different and are selected independently of one another
R1、R2Are identical or different and are selected independently of one another
Wherein the content of the first and second substances,and (b) represents a connection site.
The invention provides a fluorescent material, which is formed by self-assembly of a compound shown in a formula (I).
According to an embodiment of the present invention, the fluorescent material is a hierarchical aggregate structure, preferably a hierarchical flower-like aggregate structure or a hierarchical spherical aggregate structure.
According to an embodiment of the invention, the particle size of the fluorescent material is 10-100 μm, preferably 20-60 μm, and still more preferably 20-40 μm.
According to an embodiment of the invention, the fluorescent material has a fluorescence quantum yield of 5-50%, such as 10%, 20%, 30% or 50%.
Embodiments of the present invention also provide a method of preparing a fluorescent material as described above, comprising the steps of:
(1) reacting the compound a1 with pivaloyl diboron to obtain a compound a 2;
(2) reacting the compound a2 with the compound a3 to obtain a 4;
(3) reacting the compound a5 with pivaloyl diboron to obtain a compound a 6;
(4) reacting a compound a6 with a compound a4 to obtain a fluorene derivative shown as a formula (I);
(5) dissolving a fluorene derivative shown in a formula (I) in a good solvent, and then adding a poor solvent for self-assembly to obtain the fluorescent material;
it will be understood by those skilled in the art that when A is used1And A2When not identical, the method comprises contacting the substrate in at least one of the steps described above
Wherein R is1、R2、A1、A2N has the above-mentioned definition, wherein 6. gtoreq.m.gtoreq.1.
According to an embodiment of the invention, steps (1) and (3) are carried out in a catalyst system.
According to an embodiment of the invention, the catalyst system comprises acetate (potassium acetate, sodium acetate) and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride.
According to an embodiment of the invention, the catalyst system may be used in an amount of: the addition amount of acetate is 1-5 equivalents and the addition amount of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is 5-20% equivalents relative to 1 equivalent of the raw material compound;
according to the embodiment of the invention, the steps (1) and (3) are carried out under the protection of inert gas, the reaction temperature is 50-100 ℃, and the reaction time is 8-12 h;
according to an embodiment of the invention, steps (2) and (4) are carried out in a catalyst system comprising tetrakis (triphenylphosphine) palladium and a carbonate (potassium carbonate, sodium carbonate or cesium carbonate). The addition amount of tetrakis (triphenylphosphine) palladium is 5-15% equivalent, and the addition amount of carbonate is 2-4 equivalent, relative to 1 equivalent of the raw material compound;
according to the embodiment of the invention, the steps (2) and (4) are carried out under the protection of inert gas, the reaction temperature is 60-90 ℃, and the reaction time is 6-10 h;
according to an embodiment of the present invention, the good solvent in step (5) is selected from haloalkane solvents;
according to an embodiment of the present invention, the poor solvent in step (5) is selected from an alcohol solvent, a ketone solvent or an alkane solvent;
according to an embodiment of the present invention, the volume ratio of the good solvent to the poor solvent is 1:5 to 1:30, preferably 1:5 to 1:20, and further preferably 1:5 to 1: 10;
according to an embodiment of the present invention, the good solvent is selected from at least one of chloroform and dichloromethane;
according to an embodiment of the present invention, the poor solvent is selected from at least one of methanol, ethanol, acetone, n-hexane;
the invention also provides application of the fluorescent material in detection of phthalate plasticizers, particularly application in detection of gas-phase phthalate plasticizers.
According to an embodiment of the present invention, the phthalate plasticizer is one or more of dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBzP), di (2-ethyl) hexyl phthalate (DEHP), di-n-octyl phthalate (DOP), and diisononyl phthalate (DiNP).
According to an embodiment of the invention, the concentration of the gas phase phthalate plasticizer in the gas phase is above 0.01 ppb.
Advantageous effects
The invention relates to a fluorene derivative fluorescent material, a preparation method thereof and application thereof in detection of gas-phase phthalate plasticizer (ppb level), wherein the fluorescence quantum yield is 5-50%. The material has a hierarchical flower-like structure and a hierarchical microsphere structure with larger surface area, and increases the surface area contacted with detection gas, so that the detection sensitivity is high (ppb level). And the material can be used for detecting whether the phthalate plasticizer is added in the actual material (such as preservative film and the like).
Definition and description of terms
Unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. Such combinations and definitions of groups and structures of compounds after combination are intended to fall within the scope of the present disclosure.
Unless otherwise indicated, the recitation of numerical ranges in the specification and claims of this application, when such numerical ranges are defined as "integers," is understood to mean that the two endpoints of the range are recited and each integer within the range is. For example, "an integer of 0 to 10" should be understood to describe each integer of 0, 1,2, 3, 4, 5, 6, 7, 8, 9, and 10.
The term "C1-12Straight-chain or branched alkyl "is understood to preferably mean a straight-chain or branched saturated hydrocarbon radical having from 1 to 12 carbon atoms, preferably C1-10An alkyl group. "C1-10Alkyl "is understood to preferably mean a straight-chain or branched saturated hydrocarbon radical having 1,2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl. In particular, the radicals have 1,2, 3, 4, 5, 6 carbon atoms ("C)1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl.
"alkyl" used herein alone or as a suffix or prefix is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having from 1 to 20 carbon atoms (or a specific number of carbon atoms if provided). For example, "C1-C8Alkyl "denotes straight-chain and branched alkyl groups having 1,2, 3, 4, 5, 6, 7 or 8 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.
"alkenyl" used alone or as suffix or prefix in the present invention is intended to include compounds having from 2 to20 carbon atoms (a particular number of carbon atoms, if provided, is intended to mean that particular number) of branched and straight chain aliphatic hydrocarbon groups comprising an alkenyl or alkene. For example, "C2-6Alkenyl "denotes alkenyl having 2,3, 4, 5 or 6 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, 3-methylbut-1-enyl, 1-pentenyl, 3-pentenyl, and 4-hexenyl.
The term "cycloalkyl" as used herein is intended to include saturated cyclic groups having the specified number of carbon atoms. These terms may include fused or bridged polycyclic ring systems. Cycloalkyl groups have 3 to 40 carbon atoms in their ring structure. In one embodiment, the cycloalkyl group has 3, 4, 5, or 6 carbon atoms in its ring structure. For example, "C3-6Cycloalkyl "denotes a group such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
The term "aryl" as used herein refers to an aromatic ring structure made up of 5 to 20 carbon atoms. For example: the aromatic ring structure containing 5, 6, 7 and 8 carbon atoms may be a monocyclic aromatic group such as phenyl; the ring structure containing 8, 9, 10, 11, 12, 13 or 14 carbon atoms may be polycyclic, for example naphthyl. The aromatic ring may be substituted at one or more ring positions with those substituents described above. The term "aryl" also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (the rings are "fused rings"), wherein at least one of the rings is aromatic and the other cyclic rings can be, for example, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and/or heterocyclyl. Examples of polycyclic rings include, but are not limited to, 2, 3-dihydro-1, 4-benzodioxine and 2, 3-dihydro-1-benzofuran.
As used herein, "heteroaryl" refers to a heteroaromatic heterocycle having at least one ring heteroatom (e.g., sulfur, oxygen, or nitrogen). Heteroaryl groups include monocyclic ring systems and polycyclic ring systems (e.g., having 2,3, or 4 fused rings). Examples of heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, quinolinyl, isoquinolinyl, thienyl, imidazolyl, thiazolyl, indolyl, pyrrolyl, oxazolyl, benzofuryl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, triazolyl, tetrazolyl, indazolyl, 1,2, 4-thiadiazolyl, isothiazolyl, benzothienyl, purinyl, carbazolyl, benzimidazolyl, benzoxazolyl, azabenzoxazolyl, imidazothiazolyl, benzo [1,4] dioxanyl, benzo [1,3] dioxolyl, and the like. In some embodiments, heteroaryl groups have from 3 to 40 carbon atoms and in other embodiments from 3 to 20 carbon atoms. In some embodiments, heteroaryl groups contain 3 to 14, 4 to 14, 3 to 7, or 5 to 6 ring-forming atoms. In some embodiments, heteroaryl has 1 to 4, 1 to 3, or 1 to 2 heteroatoms. In some embodiments, the heteroaryl group has 1 heteroatom.
The term "heterocyclyl", as used herein, unless otherwise specified, refers to a saturated, unsaturated or partially saturated monocyclic, bicyclic or tricyclic ring containing from 3 to 20 atoms, wherein 1,2, 3, 4 or 5 ring atoms are selected from nitrogen, sulfur or oxygen, which, unless otherwise specified, may be attached through carbon or nitrogen, wherein-CH is2-the group is optionally replaced by-c (o) -; and wherein unless otherwise stated to the contrary, the ring nitrogen atom or the ring sulfur atom is optionally oxidized to form an N-oxide or S-oxide or the ring nitrogen atom is optionally quaternized; wherein-NH in the ring is optionally substituted with acetyl, formyl, methyl or methanesulfonyl; and the ring is optionally substituted with one or more halogens. It is understood that when the total number of S and O atoms in the heterocyclic group exceeds 1, these heteroatoms are not adjacent to each other. If the heterocyclyl is bicyclic or tricyclic, at least one ring may optionally be a heteroaromatic ring or an aromatic ring, provided that at least one ring is non-heteroaromatic. If the heterocyclic group is monocyclic, it is not necessarily aromatic. Examples of heterocyclyl groups include, but are not limited to, piperidinyl, N-acetylpiperidinyl, N-methylpiperidinyl, N-formylpiperazinyl, N-methylsulfonylpiperazinyl, homopiperazinyl, piperazinyl, azetidinyl, oxetanyl, morpholinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, indolinyl, tetrahydropyranyl, dihydro-2H-pyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiopyran-1-oxide, tetrahydrothiopyran-1, 1-dioxideSubstance, 1H-pyridin-2-one and 2, 5-dioxoimidazolidinyl.
The term "inert gas" as used herein includes gases inert to the reaction, such as nitrogen and noble gases, unless otherwise specified.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of Compound 1 in example 1 of the present invention.
FIG. 2 shows a mass spectrum of Compound 1 in example 1 of the present invention.
FIG. 3. Compound 1 in example 1 of the present invention was purified in chloroform: scanning electron microscope pictures of hierarchical flower-like structure aggregates formed by self-assembly under methanol (1: 10) conditions.
FIG. 4 is a graph showing an ultraviolet-visible absorption spectrum of Compound 1 in chloroform in example 1 of the present invention.
FIG. 5. Compound 1 in example 1 of the present invention was purified in chloroform: fluorescence spectra of hierarchical flower-like aggregates formed by self-assembly in methanol (1: 10).
FIG. 6. Compound 1 in example 3 of the present invention was purified from chloroform: the fluorescence change time charts of the hierarchical flower-like structure aggregates formed by self-assembly under methanol (1: 10) for different concentrations of dimethyl phthalate (DMP) vapor.
FIG. 7. Compound 1 in example 4 of the invention in chloroform: the fluorescence change time diagram of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for diethyl phthalate (DEP) steam with different concentrations.
FIG. 8. Compound 1 in example 5 of the present invention was purified from chloroform: a fluorescence change time chart of a hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for dipropyl phthalate (DPP) steam with different concentrations is shown.
FIG. 9. Compound 1 in example 6 of the invention in chloroform: a time chart of fluorescence change of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) to dibutyl phthalate (DBP) steam with different concentrations is shown.
FIG. 10. Compound 1 in example 7 of the invention in chloroform: a time chart of fluorescence change of a hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) to steam of butyl benzyl phthalate (BBzP) with different concentrations.
Figure 11. in example 8 of the invention, compound 1 was purified in chloroform: a graph of fluorescence change profiles of hierarchical flower-like aggregates formed by self-assembly under methanol (1: 10) for different concentrations of bis (2-ethylhexyl) phthalate (DEHP) vapor.
Figure 12. in example 9 of the invention, compound 1 was purified in chloroform: the fluorescence change time chart of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for different concentrations of di-n-octyl phthalate (DOP) steam.
FIG. 13. Compound 1 in example 10 of the present invention was purified from chloroform: graph showing fluorescence change of hierarchical flower-like structure aggregates formed by self-assembly under methanol (1: 10) for different concentrations of diisononyl phthalate (DiNP) vapor.
FIG. 14. in example 11 of the present invention, Compound 1 was purified in chloroform: a time chart of fluorescence change of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for different concentrations of 1, 4-dioxane vapor.
Figure 15. in example 12 of the invention, compound 1 was purified in chloroform: the fluorescence change time charts of the hierarchical flower-like structure aggregates formed by self-assembly under methanol (1: 10) for different concentrations of HCl vapor.
Figure 16. in example 13 of the invention, compound 1 was purified in chloroform: the fluorescence change time chart of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for aniline vapor with different concentrations.
Figure 17. in example 14 of the invention, compound 1 was purified in chloroform: the fluorescence change time chart of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for phenylethylamine vapor with different concentrations.
Figure 18. in example 15 of the invention, compound 1 was purified in chloroform: the fluorescence change time chart of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for methanol steam with different concentrations.
Figure 19. in example 16 of the invention, compound 1 was purified in chloroform: a time chart of fluorescence change of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) to triethylamine steam with different concentrations is shown.
Figure 20. in example 17 of the invention, compound 1 was purified in chloroform: the fluorescence change time chart of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for ethanol steam with different concentrations.
Figure 21. in example 18 of the invention, compound 1 was purified in chloroform: the fluorescence change time chart of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for chloroform vapor with different concentrations.
Figure 22. in example 19 of the invention, compound 1 was purified in chloroform: the fluorescence change time chart of the hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) for water vapor with different concentrations.
Figure 23. in example 20 of the invention, compound 1 was purified in chloroform: a time chart of fluorescence change of a hierarchical flower-like structure aggregate formed by self-assembly under the condition of methanol (1: 10) to preservative film steam containing a phthalate plasticizer is shown.
FIG. 24 shows a nuclear magnetic spectrum of
FIG. 25 is a mass spectrum of
FIG. 26. in example 2 of the present invention,
Figure 27. in example 21 of the invention,
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
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