阅读说明：本技术 一种具有光降解功能的酰肼物质及其制备方法和应用 (Hydrazide substance with photodegradation function and preparation method and application thereof ) 是由 李智慧 李大爱 赵琳 李钟玉 于 2021-09-03 设计创作，主要内容包括：本发明公开了一种具有光降解功能的酰肼物质及其制备方法和应用。其制备方法分别是：将2-硝基苯甲醛或2-硝基-1,4-对二溴苄先与3-巯基丙酸甲酯在室温条件下,用乙酸乙酯或者二氯甲烷作溶剂,选择对应的催化剂,催化得到酯类的产物,将其用于与水合肼反应,得到对应的酰肼物质。该方法制备过程简单,在高分子合成领域内有广泛的应用前景。(The invention discloses a hydrazide substance with a photodegradation function, a preparation method and application thereof. The preparation method comprises the following steps: 2-nitrobenzaldehyde or 2-nitro-1, 4-p-dibromide benzyl and 3-mercapto methyl propionate are firstly catalyzed by using ethyl acetate or dichloromethane as a solvent under the condition of room temperature to obtain an ester product, and the ester product is used for reacting with hydrazine hydrate to obtain a corresponding hydrazide substance. The method has simple preparation process and wide application prospect in the field of polymer synthesis.)

1. A hydrazide material having a photodegradable function, which comprises:

the molecular formula is as follows:

2. the method for producing a hydrazide substance having a photodegradation function as claimed in claim 1, wherein: the method comprises the following steps:

the method comprises the following steps: adding a nitrobenzene-containing compound and methyl 3-mercaptopropionate into a reaction vessel filled with a first solvent, stirring and mixing to form a first mixture, adding a catalyst, and stirring by adopting magnetic force;

step two: reacting at room temperature for 3-5h, performing reduced pressure rotary evaporation to obtain a crude product, and further purifying by adopting a column chromatography method to obtain a purified intermediate substance;

step three: dissolving the purified intermediate substance in a second solvent, adding hydrazine hydrate, stirring at 60 ℃ for 6-8 h, concentrating under reduced pressure, cooling to obtain yellow solid substance, washing with the second solvent for several times, and drying in a vacuum drying oven;

the nitrobenzene compounds are 2-nitrobenzaldehyde or 2-nitro-1, 4-p-dibromide benzyl;

the intermediate substances are as follows:

3. the method for producing a hydrazide substance having a photodegradation function as claimed in claim 2, wherein: the first solvent is ethyl acetate or dichloromethane.

4. The method for producing a hydrazide substance having a photodegradation function as claimed in claim 2, wherein: the catalyst is trifluoroacetic acid or triethylamine.

5. The method for producing a hydrazide substance having a photodegradation function as claimed in claim 2, wherein: the second solvent is ethanol.

6. The method for producing a hydrazide substance having a photodegradation function as claimed in claim 2, wherein: the mass fraction of 2-nitrobenzaldehyde in the first mixture is 20% to 50%.

7. The method for producing a hydrazide substance having a photodegradation function as claimed in claim 2, wherein: the molar charge ratio of the nitrobenzaldehyde compound to the methyl 3-mercaptopropionate is as follows: 1: 2.1-2.5.

8. The method for producing a hydrazide substance having a photodegradation function as claimed in claim 2, wherein: the adding amount of the catalyst is 0.03-0.08% of the mass of the first solvent.

9. The method for producing a hydrazide substance having a photodegradation function as claimed in claim 2, wherein: the molar charge ratio of the intermediate substance to the hydrazine hydrate is as follows: 1: 4-6;

the mass fraction of the intermediate substance in the second solvent is 5% -20%.

10. Use of the hydrazide substance having photodegradation function as claimed in claim 1, wherein: the hydrogel with the photodegradation function is prepared by the method.

Technical Field

The invention belongs to the field of organic synthesis and polymer synthesis, and particularly relates to a hydrazide substance with a photodegradation function, and a preparation method and application thereof.

Background

Hydrazide compounds are a class of widely used nitrogen heteroatom compounds, including mono-hydrazide and bis-hydrazide compounds, have very high chemical reaction performance, and are often used as synthetic precursors or intermediates in organic molecules, such as: drugs, dyes, liquid crystal materials, and the like; in addition, the hydrazide skeleton is used as a potential therapeutic drug, and has wide biological and physiological activities, such as: antivirus, antimalarial, insecticidal, antitumor, bactericidal, etc. In addition, hydrazides have strong coordination abilities and are widely used in the field of analytical disciplines. Therefore, the research on the synthesis and performance of the compounds containing hydrazide structural units draws high attention from domestic and foreign scholars.

The hydrazide compound is an important component for synthesizing the hyperbranched hydrogel in the field of macromolecules due to the particularity of the structure of the hydrazide compound, and the synthesized hydrogel has the property of reversible acid sensitivity; the material synthesized by hydrazide and aldehyde group contains acylhydrazone bonds, is a dynamic cross-linked covalent bond, is commonly used for preparing self-healing hydrogel by utilizing the characteristic, is different from common hydrogel, can automatically repair damage by activating the self-healing process so as to recover certain damage, can repeat the self-healing process in multiple cycles, thereby prolonging the service life, and can realize self-healing in room-temperature air without any external stimulation.

Therefore, in view of the many advantages of hydrazide materials, it is necessary to further broaden the application range of such compounds by reasonably designing and synthesizing based on the hydrazide skeleton and endowing the compounds with new functions. As is well known, the o-nitrobenzyl-based substance has a photodegradation function, and is also an important component for designing and synthesizing a photoresponse hydrogel or a photoresponse polymer drug carrier, which is widely used because the photoresponse hydrogel or the drug carrier has the advantage of remote control in time and space. It is considered that the introduction of an o-nitrobenzyl-based substance into a hydrazide can develop a hydrazide substance having photodegradability to impart a photodegradable function to a further application.

Disclosure of Invention

In view of the disadvantages of the prior art, the present invention aims to provide a hydrazide material with a photodegradation function.

In order to achieve the purpose, the invention provides the following technical scheme:

a hydrazide compound with a photodegradable function,

the molecular formula is as follows:

as another object of the present invention, there is provided a method for producing a hydrazide substance having a photodegradation function, comprising the steps of:

the method comprises the following steps: adding nitrobenzene-containing compounds and methyl 3-mercaptopropionate into a reaction vessel filled with a first solvent, stirring and mixing to form a first mixture, adding a catalyst, and stirring by adopting magnetic force;

step two: reacting at room temperature for 3-5h, performing reduced pressure rotary evaporation to obtain a crude product, further purifying by adopting a column chromatography method to obtain a purified intermediate substance;

step three: dissolving the purified intermediate substance in a second solvent, adding hydrazine hydrate, stirring at 60 ℃ for 6-8 h, concentrating under reduced pressure, cooling to obtain yellow solid substance, washing with the second solvent for several times, and drying in a vacuum drying oven;

the nitrobenzene-containing compound is 2-nitrobenzaldehyde or 2-nitro-1, 4-p-dibromide benzyl;

the intermediate substances are as follows:

as a further improvement of the present invention,

the first solvent is ethyl acetate or dichloromethane.

As a further improvement of the present invention,

the catalyst is trifluoroacetic acid or triethylamine.

As a further improvement of the present invention,

the second solvent is ethanol.

As a further improvement of the present invention,

the mass fraction of 2-nitrobenzaldehyde in the first mixture is 20% to 50%.

As a further improvement of the present invention,

the molar charge ratio of the nitrobenzaldehyde compound to the methyl 3-mercaptopropionate is as follows: 1: 2.1-2.5.

As a further improvement of the present invention,

the adding amount of the catalyst is 0.03-0.08% of the mass of the first solvent.

As a further improvement of the present invention,

the molar charge ratio of the intermediate substance to the hydrazine hydrate is as follows: 1: 4-6;

the mass fraction of the intermediate substance in the second solvent is 5% -20%.

Another object of the present invention is to provide a use of a hydrazide having a photodegradation function, which comprises: the hydrogel with the photodegradation function is prepared by the method.

Particularly, when 2-nitrobenzaldehyde is selected as a raw material, mixing is carried out in a first solvent which is easy to be partially, the first solvent is most preferably ethyl acetate, and the catalyst is most preferably trifluoroacetic acid; when 2-nitro-1, 4-p-dibromide benzyl is selected, the first solvent is most preferably dichloromethane, and the catalyst is most preferably triethylamine.

The principle of the invention is as follows: 2-nitrobenzaldehyde or 2-nitro-1, 4-p-dibromide and 3-mercaptopropionic acid methyl ester react to generate ester substances, and then the ester substances react with hydrazine hydrate at 60 ℃ to obtain hydrazide substances, wherein the reaction route is as follows:

the invention has the beneficial effects that:

1. the method has the advantages of cheap and easily-obtained raw materials, high reaction rate, mild reaction conditions and simple and easy operation;

2. the monomer substance obtained by the invention has an o-nitrobenzyl structure and photosensitive property, can be degraded by ultraviolet irradiation to generate aldehyde substances, and mainly generates aldehyde groups on a benzyl position.

3. The hydrogel synthesized by the photodegradable hydrazide substance has photodegradable performance and obvious effect.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of an o-nitrobenzaldehyde thional methyl propionate substance obtained by using 2-nitrobenzaldehyde provided in example 1 of the present invention as a reactant;

FIG. 2 is a nuclear magnetic hydrogen spectrum of an o-nitrobenzaldehyde mercaptal propionyl hydrazine substance provided in example 1 before and after ultraviolet irradiation;

FIG. 3 is a nuclear magnetic hydrogen spectrum of a methyl o-nitro-p-dibenzyl sulfide propionate product obtained by using 2-nitro-1, 4-p-dibenzyl bromide provided in example 2 of the present invention as a reactant;

FIG. 4 is a nuclear magnetic hydrogen spectrum of o-nitro-p-dibenzyl sulfide propionyl hydrazine substance provided in example 2 of the present invention;

FIG. 5 is a reaction scheme for preparing a hydrogel from a hydrazide material having a photodegradation function as provided in example 3 of the present invention;

FIG. 6 is a graph showing the appearance of a hydrogel prepared from a hydrazide material having a photodegradation function provided in example 3 of the present invention.

FIG. 7 is a graph showing the appearance of a hydrogel prepared from a hydrazide material having a photodegradation function according to example 3 of the present invention before and after UV irradiation.

FIG. 8 is an appearance diagram of a hydrogel prepared by using a hydrazide substance having a photodegradation function and added with hydrogen peroxide, provided in example 3 of the present invention.

FIG. 9 is a nuclear magnetic spectrum of a hydrogel prepared from a hydrazide material with a photodegradation function provided in example 3 of the present invention after ultraviolet irradiation.

Detailed Description

The invention will be further described in detail with reference to the following examples, which are given in the accompanying drawings.

Example 1

The method comprises the following steps: 3.02g of 2-nitrobenzaldehyde was dissolved in 12g of ethyl acetate, and after dissolution, 5.52g of methyl 3-mercaptopropionate and 6mg of trifluoroacetic acid were added, and the mixture was placed in a water bath and stirred by magnetic force.

Step two: tracking reaction progress by thin layer chromatography, after the reaction is finished, performing rotary evaporation on the system under reduced pressure to obtain a crude product, further purifying by column chromatography, wherein a developing agent is ethyl acetate petroleum ether (the volume ratio is 1: 4), and passing through a column. Collecting target points and concentrating to obtain a pure o-nitrobenzaldehyde mercaptal methyl propionate substance.

Taking 20mg of pure o-nitrobenzaldehyde mercaptal methyl propionate substance, dissolving the substance by using deuterated chloroform, and performing nuclear magnetism treatment, wherein nuclear magnetism information is shown in figure 1:¹H NMR(400MHz，CDCl₃)δ8.03-7.97(m，1H)，7.93-7.87(m，1H)，7.66(dd，J＝10.8，4.5Hz，1H)，7.50-7.43(m，1H)，5.85(d，J＝2.5Hz，1H)，3.71(d，J＝2.7Hz，6H)，2.99-2.90(m，2H)，2.84(dtd，J＝9.7，7.2，2.7Hz，2H)，2.65(td，J＝7.1，2.2Hz，4H).

step three: and (3) putting 3.0g of the o-nitrobenzaldehyde mercaptal methyl propionate substance obtained in the step two into 30g of ethanol, adding 2.41g of hydrazine hydrate with 6 equivalents into the system by adopting magnetic stirring, stirring for 6h at 60 ℃, concentrating, cooling to show that a light yellow solid substance appears, washing for a plurality of times by using ethanol, collecting yellow insoluble substances, and drying for later use.

Step four: taking 40mg of the hydrazide substance in the fourth step into deuterated dimethyl sulfoxide, halving, respectively carrying out ultraviolet-free irradiation and nuclear magnetic resonance on the first part, wherein the nuclear magnetic resonance information is shown as A in figure 2:¹H NMR(400MHz，DMSO)δ9.07(d，J＝11.3Hz，2H)，7.97(dd，J＝8.1，1.0Hz，1H)，7.93-7.87(m，1H)，7.80(t，J＝7.6Hz，1H)，7.63-7.57(m，1H)，5.70-5.60(m，1H)，4.22(s，4H)，2.84(dt，J＝13.2，7.4Hz，2H)，2.78-2.68(m，2H)，2.39-2.29(m，4H).

the other part is irradiated by ultraviolet light for 6min, as shown in B in figure 2, the nuclear magnetism is applied, and the hydrogen peak on the aldehyde group appears at 9.88ppm, and the hydrogen peak on the benzene ring also has new change, which is caused by the aldehyde product generated by photodegradation, and indicates that the substance can be photodegraded.

Example 2

The method comprises the following steps: 2.6g of 2-nitro-1, 4-p-dibromobenzyl is dissolved in 8.7g of dichloromethane, 2.32g of methyl 3-mercaptopropionate is added after the dissolution, and 1.96g of triethylamine is slowly added dropwise to the system by magnetic stirring.

Step two: tracking the reaction progress by adopting a thin layer chromatography, after the reaction is finished, carrying out reduced pressure rotary evaporation to obtain a crude product, enabling the crude product to pass through a column by adopting a column chromatography method, adopting a mixed solution (the volume ratio is 1: 3) of ethyl acetate petroleum ether as a developing agent, passing through the column, collecting a target point and concentrating to obtain a pure o-nitro-p-dibenzylthioether methyl propionate product. As shown in fig. 3, the obtained nuclear magnetic information is:¹H NMR(400MHz，CDCl₃)δ7.97(s，1H)，7.56(d，J＝7.8Hz，1H)，7.48(d，J＝7.8Hz，1H)，4.10(s，2H)，3.81(s，2H)，3.72(d，J＝4.5Hz，6H)，2.75(dd，J＝13.4，6.9Hz，4H)，2.60(dd，J＝12.7，6.6Hz，4H).

step three: and (3) putting 2.38g of the methyl o-nitro-p-dibenzyl sulfide propionate product obtained in the step two into 23.8g of ethanol, adding 1.84g of hydrazine hydrate with 6 equivalents into the system by magnetic stirring, stirring for 6 hours at 60 ℃, carrying out reduced pressure concentration to obtain yellow solid matters, washing the yellow solid matters for several times by ethanol, collecting yellow insoluble matters, and drying the yellow insoluble matters for later use.

Step four: taking 20mg of the hydrazide substance in the third step in deuterated dimethyl sulfoxide, performing nuclear magnetic resonance, and obtaining nuclear magnetic resonance information as shown in figure 4:¹H NMR(400MHz，DMSO)δ9.06(d，J＝5.8Hz，2H)，8.00(d，J＝1.6Hz，1H)，7.66(dd，J＝7.9，1.7Hz，1H)，7.58(d，J＝7.8Hz，1H)，4.22(s，4H)，4.05(s，2H)，3.86(s，2H)，2.61(td，J＝7.3，4.9Hz，4H)，2.31(dt，J＝14.3，7.2Hz，4H)。

example 3

Step A: 0.18g of hydrazide material in example 1 and 1g of polyethylene glycol diacrylate (number average molecular weight 1000) are taken in water, the mass fraction of solute is controlled to be 17.8%, a little is taken out of a sealed tube, the reaction is carried out for 34h at 65 ℃, the system does not flow any more, the reaction route is shown in figure 5, and the obtained reaction product is shown in figure 6.

And B: taking a little of the hydrogel obtained in step A, as shown in A of FIG. 7, and exposing it to UV light for 3min, the hydrogel was changed from the original gel state to a fluid state, as shown in B of FIG. 7, indicating that the hydrogel was indeed degraded.

And C: because the hydrogel has a material structure containing an o-nitro structure, the hydrogel can generate a photodegradation function, and simultaneously because the hydrogel also contains a mercaptal structure, the hydrogel can be oxidized by hydrogen peroxide. Taking the hydrogel obtained in the step A (about 36mg), adding a few drops of hydrogen peroxide into the hydrogel as shown in a diagram in fig. 8, and changing the hydrogel from the original gel state into liquid after 20 hours, as shown in a diagram B in fig. 8, which shows that the hydrogel containing mercaptal bonds can also be degraded by hydrogen peroxide.

Step D: and D, freeze-drying the hydrogel obtained in the step A, weighing 15mg of the dried hydrogel in deuterated DMSO, placing the hydrogel in a deuterated DMSO, irradiating the hydrogel for 6min under an ultraviolet lamp, performing nuclear magnetism, and obtaining a nuclear magnetism information map as shown in figure 9.

The principle of the invention is as follows: 2-nitrobenzaldehyde or 2-nitro-1, 4-p-dibromide and 3-mercaptopropionic acid methyl ester react to generate ester substances, and then the ester substances react with hydrazine hydrate at 60 ℃ to obtain hydrazide substances, wherein the reaction route is as follows:

the invention has the beneficial effects that:

1. the method has the advantages of cheap and easily-obtained raw materials, high reaction rate, mild reaction conditions and simple and easy operation;

2. the monomer substance obtained by the invention has an o-nitrobenzyl structure and photosensitive property, can be degraded by ultraviolet irradiation to generate aldehyde substances, and mainly generates aldehyde groups on a benzyl position.

3. The hydrogel synthesized by the photodegradable hydrazide substance has photodegradable performance and obvious effect.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.