阅读说明：本技术 一种化合物和荧光物质、其制备方法、及酸碱指示剂 (Compound and fluorescent substance, preparation method thereof and acid-base indicator ) 是由 崔国友 姜玉柱 于 2020-04-29 设计创作，主要内容包括：本发明公开了一种化合物和荧光物质、其制备方法、及酸碱指示剂,通过将酚类化合物与含有多胺基的化合物反应,生成包含由多个六元环所形成共轭结构的化合物或荧光物质,其中,共轭结构包括含氮六元环,共轭结构使得化合物或荧光物质具有荧光性能。当在酸性条件下,共轭结构中的氮与氢离子结合,从而破坏了共轭结构,致使荧光强度变弱甚至荧光性能消失。(The invention discloses a compound and a fluorescent substance, a preparation method thereof and an acid-base indicator, wherein a phenolic compound is reacted with a compound containing polyamine to generate the compound or the fluorescent substance containing a conjugated structure formed by a plurality of six-membered rings, wherein the conjugated structure comprises a nitrogen-containing six-membered ring, and the conjugated structure ensures that the compound or the fluorescent substance has fluorescence property. Under acidic conditions, nitrogen in the conjugated structure is combined with hydrogen ions, so that the conjugated structure is destroyed, and the fluorescence intensity is weakened or even the fluorescence performance disappears.)

1. A compound selected from the group consisting of:

2. a process for preparing a compound of claim 1, comprising:

adding hydroquinone or catechol and ethylenediamine into a solvent consisting of any one or a combination of methanol, ethanol and water, controlling the temperature to be 0-100 ℃, and reacting for more than 0.5 hour in the presence of air or an oxidant;

generating solid in the reaction process, and filtering reaction liquid after the reaction is finished;

evaporating to remove the solvent and unreacted ethylenediamine in the filtrate to obtain a concentrated substance;

and combining the concentrated substance and the filter cake, and performing column chromatography purification by using ethanol as an eluent to obtain the compound.

3. The method according to claim 2, wherein the reaction temperature is room temperature.

4. A method for producing a fluorescent substance, comprising:

mixing any one or combination of hydroquinone, resorcinol, catechol, dopamine and dopamine derivatives withReacting any one or the combination of polyethyleneimine and cyclic ethylamine in a solvent for more than 0.5 hours in the presence of air or an oxidant at the temperature of 0-100 ℃;

separating to obtain a solid generated by the reaction;

wherein n is a positive integer, R₁、R₂Each independently selected from H or alkyl.

5. The method according to claim 4, wherein the reaction temperature is room temperature.

6. The method according to claim 4, wherein the reaction solvent is any one or a combination of methanol, ethanol and water.

7. The method according to any one of claims 4 to 6, wherein R is₁And R₂Are all H.

8. The method according to claim 7, wherein n is 1 or 3.

9. A fluorescent substance obtained by the production method according to any one of claims 4 to 8.

10. An acid-base indicator comprising the compound according to claim 1 or the fluorescent substance according to claim 9.

Technical Field

The invention relates to the technical field of acid-base detection, in particular to a compound, a fluorescent substance, a preparation method of the compound and the fluorescent substance, and an acid-base indicator.

Background

Fluorescent compounds or fluorescent polymers have been widely studied in the fields of biochemistry, environmental science, molecular biology, and the like, and have been widely used in the fields of pharmaceutical carriers, fluorescent probes, fluorescent images, fluorescent chemical sensors, and luminescent materials. Multifunctional fluorescent materials, for example: fluorescent group materials which have temperature sensitivity or acid-base sensitivity and can be flexibly regulated and controlled are sought by people.

Phenolic compounds and amine compounds are two common types of compounds and are widely used in chemical synthesis. However, in the related art, the amino benzoquinone-type material synthesized by the amino compound and the phenolic compound has no fluorescence property.

Disclosure of Invention

In view of the above-mentioned deficiencies in the related art, embodiments of the present invention provide a compound and a fluorescent substance, a method for preparing the same, and an acid-base indicator.

According to one aspect of the present invention, there is provided a compound selected from:

accordingly, the present invention also provides a process for the preparation of a compound as described above, comprising the steps of:

adding hydroquinone or catechol and ethylenediamine into a solvent consisting of any one or a combination of methanol, ethanol and water, controlling the temperature to be 0-100 ℃, and reacting for more than 0.5 hour in the presence of air or an oxidant;

generating solid in the reaction process, and filtering reaction liquid after the reaction is finished;

evaporating to remove the solvent and unreacted ethylenediamine in the filtrate to obtain a concentrated substance;

and combining the concentrated substance and the filter cake, and performing column chromatography purification by using ethanol as an eluent to obtain the compound.

Alternatively, in the preparation method of the above compound provided in the embodiment of the present invention, the reaction temperature is room temperature.

According to another aspect of the present invention, there is provided a method of preparing a fluorescent substance, comprising the steps of:

mixing any one or combination of hydroquinone, resorcinol, catechol, dopamine and dopamine derivatives withAny one or the combination of polyethyleneimine and cyclic ethylamine in a solventReacting for more than 0.5 hour in the presence of air or oxidant at the temperature of 0-100 ℃;

separating to obtain a solid generated by the reaction;

wherein n is a positive integer, R₁、R₂Each independently selected from H or alkyl.

Alternatively, in the method for producing the above fluorescent substance provided in the embodiment of the present invention, the reaction temperature is room temperature.

Alternatively, in the method for preparing the fluorescent substance, provided by the embodiment of the present invention, the reaction solvent is any one of methanol, ethanol and water, or a combination thereof.

Alternatively, in the method for producing the above fluorescent substance provided in the embodiment of the present invention, R₁And R₂Are all H.

Alternatively, in the method for producing the above fluorescent substance provided in the embodiment of the present invention, n is 1 or 3.

Accordingly, the present invention also provides a fluorescent substance obtained by the above method for producing a fluorescent substance.

According to another aspect of the present invention, there is provided an acid-base indicator comprising the above compound or the above fluorescent substance.

The invention has the following beneficial effects:

according to the embodiment of the invention, the phenolic compound and the compound containing the polyamine group are reacted to generate the compound or the fluorescent substance containing a conjugated structure formed by a plurality of six-membered rings, wherein the conjugated structure comprises a nitrogen-containing six-membered ring, and the conjugated structure enables the compound or the fluorescent substance to have fluorescence property. Under acidic conditions, nitrogen in the conjugated structure is combined with hydrogen ions, so that the conjugated structure is destroyed, and the fluorescence intensity is weakened or even the fluorescence performance disappears.

Drawings

FIG. 1 is a fluorescence spectrum of a compound provided in example 1 of the present invention;

FIG. 2 is a fluorescence spectrum of a compound provided in example 2 of the present invention;

FIG. 3 is a fluorescence spectrum of a fluorescent substance provided in example 3 of the present invention;

FIG. 4 is a fluorescence spectrum of a fluorescent substance provided in example 4 of the present invention;

FIG. 5 is a fluorescence spectrum of a fluorescent substance provided in example 5 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.

Embodiments of the invention provide a compound selected from the group consisting of:

in the compound provided by the invention, the conjugated structure formed by three six-membered rings enables the compound to have fluorescence property. Under acidic conditions, nitrogen in the conjugated structure is combined with hydrogen ions, so that the conjugated structure is destroyed, and the fluorescence intensity of the compound is weakened or even the fluorescence performance disappears.

Correspondingly, the invention also provides a preparation method of the compound, which comprises the following steps:

adding hydroquinone or catechol and ethylenediamine into a solvent composed of any one or a combination of methanol, ethanol and water, controlling the temperature to 0-100 ℃ (e.g. 0-30 ℃, 60-80 ℃,0 ℃, 10 ℃, 15 ℃, 18 ℃, 20 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃), and reacting for more than 0.5 hours (e.g. 1 hour, 3 hours, 8 hours, 12 hours and 24 hours) in the presence of air or an oxidant;

generating solid in the reaction process, and filtering reaction liquid after the reaction is finished;

evaporating to remove the solvent and unreacted ethylenediamine in the filtrate to obtain a concentrated substance;

and combining the concentrated substance and the filter cake, and performing column chromatography purification by using ethanol as an eluent to obtain the compound.

The above compounds are only examples provided by the present invention and do not cover all compounds obtained by the preparation method according to the present invention, and therefore, any compounds obtained by the preparation method according to the present invention are included in the scope of the present invention.

Alternatively, in the preparation method of the above compound provided in the embodiment of the present invention, the reaction temperature is room temperature.

It can be understood that the reaction is carried out at room temperature, the operation is convenient, the energy is saved, the reaction is mild, and the danger is small. The room temperature in the present invention is generally about 25 ℃, for example, 16 to 18 ℃ in winter and 24 to 26 ℃ in summer.

According to another aspect of the present invention, there is provided a method of preparing a fluorescent substance, comprising the steps of:

mixing any one or combination of hydroquinone, resorcinol, catechol, dopamine and dopamine derivatives withReacting one or a combination of polyethyleneimine and cyclic ethylamine in a solvent in the presence of air or an oxidant for 0.5 hour or more (e.g., 1 hour, 3 hours, 8 hours, 12 hours, and 24 hours) at a reaction temperature of 0 ℃ to 100 ℃ (e.g., 0 ℃ to 30 ℃, 60 ℃ to 80 ℃,0 ℃, 10 ℃, 15 ℃, 18 ℃, 20 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, and 100 ℃);

separating to obtain a solid generated by the reaction;

wherein n is a positive integer, R₁、R₂Each independently selected from H or alkyl.

The phenolic compounds and polyamino compounds include, but are not limited to, the phenolic compounds and polyamino compounds listed above, and other phenolic compounds and polyamino compounds not listed that are capable of undergoing the above polymerization reaction may also be selected and included in the scope of the present invention.

Alternatively, in the method for producing the above fluorescent substance provided in the embodiment of the present invention, the reaction temperature is room temperature.

It can be understood that the reaction is carried out at room temperature, the operation is convenient, the energy is saved, the reaction is mild, and the danger is small. The room temperature in the present invention is generally about 25 ℃, for example, 16 to 18 ℃ in winter and 24 to 26 ℃ in summer.

Alternatively, in the method for preparing the fluorescent substance, provided by the embodiment of the present invention, the reaction solvent is any one of methanol, ethanol and water, or a combination thereof.

Alternatively, in the method for producing the above fluorescent substance provided in the embodiment of the present invention, R₁And R₂Are all H.

Alternatively, in the method for producing the above fluorescent substance provided in the embodiment of the present invention, n is 1 or 3.

Accordingly, the present invention also provides a fluorescent substance obtained by the above method for producing a fluorescent substance.

In the above fluorescent substance provided by the present invention, the fluorescent substance has fluorescence properties due to a conjugated structure formed by a plurality of six-membered rings. Under acidic conditions, nitrogen in the conjugated structure is combined with hydrogen ions, thereby destroying the conjugated structure, and weakening the fluorescence intensity of the fluorescent material or even eliminating the fluorescence property.

According to another aspect of the present invention, there is provided an acid-base indicator comprising the above compound or the above fluorescent substance.