阅读说明：本技术 1-（（5-叔丁基-2-羟基苯胺）亚甲基）-2-萘酮及其制备方法和应用 (1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone and preparation method and application thereof ) 是由 邢爱萍 曾岱 苑娟 褚意新 韩红艳 王新灵 张淑玲 于 2020-07-24 设计创作，主要内容包括：本发明公开了1-((5-叔丁基-2-羟基苯胺)亚甲基)-2-萘酮及其制备方法和应用,该化合物以2-羟基-1-萘甲醛和2-氨基-4-叔丁基酚为原料,以无水乙醇或甲醇为溶剂,制备而成。本发明制备的1-((5-叔丁基-2-羟基苯胺)亚甲基)-2-萘酮,对DPPH自由基具有较强的抑制作用,远远高于维生素E对DPPH自由基的抑制作用。这表明,本发明的1-((5-叔丁基-2-羟基苯胺)亚甲基)-2-萘酮具有良好的抗氧化作用,可有效用于制备抗衰老药物,是延缓衰老药物上的创新。本发明的合成工艺简单、操作方便,原料易得且生产成本低,易于工业化生产,具有很好的社会和经济效益。(The invention discloses 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone and a preparation method and application thereof, and the compound is prepared by taking 2-hydroxy-1-naphthaldehyde and 2-amino-4-tert-butylphenol as raw materials and absolute ethyl alcohol or methyl alcohol as a solvent. The 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone prepared by the invention has stronger inhibition effect on DPPH free radicals, which is far higher than the inhibition effect of vitamin E on DPPH free radicals. The result shows that the 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone has good antioxidation, can be effectively used for preparing the anti-aging drug, and is an innovation in the anti-aging drug. The invention has the advantages of simple synthesis process, convenient operation, easily obtained raw materials, low production cost, easy industrial production and good social and economic benefits.)

1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone characterized by the following structural formula:

2. the method for preparing 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone according to claim 1, characterized in that 2-amino-4-tert-butylphenol and 2-hydroxy-1-naphthaldehyde are used as reaction raw materials, absolute ethyl alcohol or methanol is used as a reaction solvent, and the 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone is prepared by reflux reaction.

3. The preparation method according to claim 2, comprising the following steps:

(1) mixing 2-amino-4-tert-butyl phenol, 2-hydroxy-1-naphthaldehyde and absolute ethyl alcohol or methanol, and carrying out reflux reaction;

(2) and (3) carrying out suction filtration on the reaction liquid to obtain a solid, washing, drying and recrystallizing to obtain brick-red solid powder, namely the 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone.

4. The production method according to claim 2 or 3, wherein the molar ratio of 2-amino-4-tert-butylphenol to 2-hydroxy-1-naphthaldehyde is 1.0 to 1.2: 1.0 to 1.2; (2-amino-4-tert-butylphenol and 2-hydroxy-1-naphthaldehyde): the mass ratio of (absolute ethyl alcohol or methanol) is 1: 40-150.

5. The method according to claim 4, wherein the molar ratio of 2-amino-4-tert-butylphenol to 2-hydroxy-1-naphthaldehyde is 1:1.

6. the preparation method according to claim 2 or 3, wherein the temperature of the reflux reaction is 75-85 ℃ and the time is 7-10 h.

7. The method according to claim 3, wherein the washing and recrystallization are carried out using absolute ethanol as a solvent.

8. The preparation method according to claim 3, further comprising purifying brick red solid powder, namely completely dissolving the brick red solid powder in methanol, stirring for 1-2 h, filtering, and naturally volatilizing the filtrate until rod-like crystals are separated, namely the purified 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone.

9. Use of 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone according to claim 1 in the preparation of a medicament for inhibiting DPPH free radicals.

10. Use of 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone according to claim 1 in the preparation of an antioxidant.

Technical Field

The invention relates to 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone and a preparation method and application thereof, belonging to the field of medicines.

Background

The radical refers to a chemical atom, molecule or group having unpaired electrons and active properties, and is a radical related to living organisms, mainly including radicals centered on N, S, O, C, H and transition metals. Under normal conditions, the organism has rich antioxidant enzymes (such as SOD and GSH-P) which can well remove redundant free radicals in the organism to keep the organism healthy, and if the balance is broken under pathological conditions, the free radicals can attack other tissues and cells to obtain paired electrons, and diseases such as senile dementia, cardiovascular diseases, coronary heart disease, tumor and the like can be caused. The reaction of free radicals is a chain reaction, and when two free radicals are combined into an electron pair, the reaction is stopped, thereby delaying the internal aging of the organism and preventing certain diseases. Although the existing antioxidant has good antioxidant effect, the existing antioxidant also has some defects, and some antioxidants have toxic and side effects, so that the synthesis of the compound with high efficiency and low toxicity and antioxidant activity through chemical reaction has great significance.

The current methods for free radical scavenging are mainly classified into two types, one is an in vitro model, and the other is an in vivo model, wherein the DPPH method is the most common method in the in vitro model. The DPPH free radical can generate a resonance stabilizing effect, and a single electron on an N atom and a benzene ring form p-pi conjugation, so that the DPPH free radical has better stability. The DPPH radical with single electron has strong absorption at 517nm, and the ethanol solution of the DPPH radical has a dark purple color. When the antioxidant is added into the solution, the free radicals and the antioxidant generate single electron pairing, so that DPPH free radicals are reduced into yellow DPPH-H molecules, the color of the solution fades, the fading degree and the number of the accepted electrons form a quantitative relation, and quantitative analysis can be carried out through the change of absorbance. When DPPH radicals react with antioxidants, the absorbance at a wavelength of 517nm decreases, the extent of which is quantitative with respect to the electrons received (antioxidant radical scavenging activity), and can be determined spectrophotometrically.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone and a preparation method and application thereof, and the compound has a simple preparation method and good antioxidation effect.

In order to achieve the above object, one of the technical solutions of the present invention is:

1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone, having the following structural formula:

one of the technical schemes of the invention is as follows: a preparation method of 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone takes 2-amino-4-tert-butylphenol and 2-hydroxy-1-naphthaldehyde as reaction raw materials and absolute ethyl alcohol or methanol as a reaction solvent to prepare the 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone through reflux reaction. The method comprises the following specific steps:

(1) mixing 2-amino-4-tert-butyl phenol, 2-hydroxy-1-naphthaldehyde and absolute ethyl alcohol or methanol, and carrying out reflux reaction;

(2) and (3) carrying out suction filtration on the reaction liquid to obtain a solid, washing, drying and recrystallizing to obtain brick-red solid powder, namely the 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone.

The molar ratio of the 2-amino-4-tert-butylphenol to the 2-hydroxy-1-naphthaldehyde is 1.0-1.2: 1.0 to 1.2.

Preferably, the molar ratio of 2-amino-4-tert-butylphenol to 2-hydroxy-1-naphthaldehyde is 1:1.

(2-amino-4-tert-butylphenol and 2-hydroxy-1-naphthaldehyde): the mass ratio of (absolute ethyl alcohol or methanol) is 1: 40-150.

The temperature of the reflux reaction is 75-85 ℃, and the time is 7-10 h.

The reagents used for washing and recrystallization are absolute ethyl alcohol.

The preparation method further comprises the step of purifying the brick red solid powder, namely completely dissolving the brick red solid powder in methanol, stirring for 1-2 hours, filtering, and naturally volatilizing the filtrate until rod-shaped crystals are separated out, namely the purified 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone.

One of the technical schemes of the invention is as follows: application of 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone in preparing a medicine for inhibiting DPPH free radicals.

One of the technical schemes of the invention is as follows: application of 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone in preparing antioxidant is provided.

The invention has the beneficial effects that:

1. the invention takes 2-hydroxy-1-naphthaldehyde and 2-amino-4-tert-butylphenol as raw materials, and absolute ethyl alcohol or methanol as a solvent to prepare the 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone, thereby effectively solving the problem of aldehyde-amine condensation.

2. The 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone prepared by the invention is a novel compound, and the compound has a naphthalene ring structure, a phenol structure and wide biological activity.

3. The 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone prepared by the invention has stronger inhibition effect on DPPH free radicals, which is far higher than the inhibition effect of vitamin E on DPPH free radicals. The result shows that the 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone has good antioxidation, can be effectively used for preparing the anti-aging drug, and is an innovation in the anti-aging drug.

4. The invention has the advantages of simple synthesis process, convenient operation, easily obtained raw materials, low production cost, easy industrial production and good social and economic benefits.

Drawings

FIG. 1 is the presentProcess for preparing 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone compound of the invention¹H NMR results chart.

FIG. 2 shows the preparation of 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone, a compound of the present invention¹³C NMR results chart.

FIG. 3 is a graph showing the infrared results of the compound 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone of the present invention.

FIG. 4 is a structural unit diagram of the compound 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone of the present invention.

FIG. 5 is a diagram showing the stacking of 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone, a compound of the present invention.

FIG. 6 is a graph comparing the antioxidant activity of the compound of the present invention, 1- ((5-tert-butyl-2-hydroxyaniline) methylene) -2-naphthalenone, as measured by DPPH, with that of vitamin E, a commonly used antioxidant.

Detailed Description

The following examples further illustrate the embodiments of the present invention in detail.