阅读说明：本技术 对集胞藻pcc6803生长具有抑制作用的含色酮苯酰腙类化合物及其制备方法 (Chromone-containing phenylhydrazone compound with inhibiting effect on growth of Synechocystis PCC6803 and preparation method thereof ) 是由 涂其冬 宋伏冰 刘米米 王莹 周庭辉 郭辉 陈道驹 向鹏 李琪 邓怡冰 于 2020-05-19 设计创作，主要内容包括：本发明提供了一种对集胞藻PCC6803生长具有抑制作用的含色酮苯酰腙类化合物及其制备方法。该化合物的分子结构如式I所示,其中R<Sup>1</Sup>选自氢、卤素、硝基、羟基、羧基、C<Sub>1</Sub>-C<Sub>4</Sub>烷基；R<Sup>2</Sup>选自氢、溴、羟基或硝基；R<Sup>3</Sup>选自氢或羟基；R<Sup>4</Sup>选自氢、卤素、硝基、三氟甲基或羟基；R<Sup>5</Sup>选自氢或羟基。在此基础上,本发明进一步提供了该化合物的制备方法,在含有乙酸的乙醇环境中,将苯甲酰肼或其取代物与3-甲酰色酮或其取代物进行反应,生成本发明化合物。该化合物对集胞藻PCC6803具有较好的生长抑制作用,EC<Sub>50</Sub>值在0.8～29.8μM范围内,可用于制备相关的抑藻剂产品。<Image he="615" wi="700" file="DDA0002498293920000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a chromone-containing phenylhydrazone compound with an inhibiting effect on the growth of synechocystis PCC6803 and a preparation method thereof. The molecular structure of the compound is shown as formula I, wherein R 1 Selected from hydrogen, halogen, nitro, hydroxy, carboxyl, C 1 ‑C 4 An alkyl group; r 2 Selected from hydrogen, bromine, hydroxyl or nitro; r 3 Selected from hydrogen or hydroxy; r 4 Selected from hydrogen, halogen, nitro, trifluoromethyl or hydroxy; r 5 Selected from hydrogen or hydroxyl. On the basis, the invention further provides a preparation method of the compound, which comprises the step of reacting benzoyl hydrazine or a substitute thereof with 3-formyl chromone or a substitute thereof in an ethanol environment containing acetic acid to generate the compound. The compound has good effect on Synechocystis PCC6803Growth inhibition of EC 50 The value is within the range of 0.8-29.8 mu M, and the product can be used for preparing related algistat products.)

1. The chromone-containing phenylhydrazone compound with the effect of inhibiting the growth of Synechocystis PCC6803 has a molecular structure shown as the following formula I:

wherein R is¹Selected from hydrogen, halogen, nitro, hydroxy, carboxyl, C₁-C₄An alkyl group;

R²selected from hydrogen, bromine, hydroxyl or nitro;

R³selected from hydrogen or hydroxy;

R⁴selected from hydrogen, halogen, nitro, trifluoromethyl or hydroxy;

R⁵selected from hydrogen or hydroxyl.

2. The chromone-containing phenylhydrazone compound having inhibitory effect on the growth of Synechocystis PCC6803 according to claim 1, wherein R is¹、R²、R³、R⁴、R⁵And the five substituents are the same or different.

3. The method for preparing the chromone-containing phenylhydrazone compound according to claim 1 or 2, wherein the method is obtained by directly reacting a compound of formula II with a compound of formula III at room temperature for 1-3 hours in an ethanol environment containing acetic acid;

4. the preparation method of claim 3, wherein after the reaction is completed, the chromone-containing phenylhydrazone compound is obtained by performing suction filtration, washing with ethanol, and drying a filter cake.

5. Use of a chromone-containing phenylhydrazone compound according to claim 1 or 2 for preparing an algistat.

6. The use of chromone-containing phenylhydrazone compound as claimed in claim 1 or claim 2 for inhibiting the growth of cyanobacteria.

7. Use according to claim 6, characterized in that said cyanobacteria is Synechocystis PCC 6803.

8. Use according to claim 7, wherein the EC for the use contains chromone phenylhydrazone compounds₅₀0.8 to 29.8 μ M.

Technical Field

The invention relates to the technical field of chemical synthesis, in particular to a chromone-containing phenylhydrazone compound with an inhibiting effect on the growth of Synechocystis PCC6803 and a preparation method thereof.

Background

With the expansion of human life and production activities in recent years, a large amount of wastewater is discharged into rivers and lakes, the eutrophication of water bodies becomes more and more serious, and blue algae are propagated suddenly to form water blooms. The blue algae will release algae toxin after death, the toxin is very stable, and the water solubility and the heat resistance are good. The algae toxin is not easy to decompose even when boiled in water at high temperature, and can not be decomposed by common tap water treatment processes (such as coagulating sedimentation, filtration and chlorination). The phycotoxin is a strong cancer promoter, can cause liver cancer, has very strong toxicity and great threat. After the blue algae bloom, the oxygen content in water is reduced, aquatic animals die in a large amount, and the damage to aquaculture is great. Therefore, how to treat the cyanobacterial bloom becomes a problem to be solved urgently. Synechocystis PCC6803 is the most important blue algae, has the highest toxicity and harm, and can effectively relieve the influence of the blue algae on the aquatic environment by using the Synechocystis PCC6803 as a killing object.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a chromone-containing phenylhydrazone compound with an inhibiting effect on the growth of Synechocystis PCC6803 and a preparation method thereof so as to solve the technical problem that the compound with the structure does not exist in the prior art.

Another technical problem to be solved by the present invention is how to achieve efficient preparation of the compound.

The invention aims to solve the technical problem of expanding the selectable range of the algistat.

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

the chromone-containing phenylhydrazone compound with the effect of inhibiting the growth of Synechocystis PCC6803 has a molecular structure shown as the following formula I:

wherein R is¹Selected from hydrogen, halogen, nitro, hydroxy, carboxyl, C₁-C₄An alkyl group;

R²selected from hydrogen, bromine, hydroxyl or nitro;

R³selected from hydrogen or hydroxy;

R⁴selected from hydrogen, halogen, nitro, trifluoromethyl or hydroxy;

R⁵selected from hydrogen or hydroxyl.

Preferably, R¹、R²、R³、R⁴、R⁵And the five substituents are the same or different.

On the basis of the technical scheme, the invention further provides a preparation method of the chromone-containing phenylhydrazone compound, which is obtained by directly reacting a compound shown in the formula II with a compound shown in the formula III at room temperature for 1-3 hours in an ethanol environment containing acetic acid;

preferably, after the reaction is finished, carrying out suction filtration, washing with ethanol, and drying a filter cake to obtain the chromone-containing phenylhydrazone compound.

On the basis of the technical scheme, the invention further provides application of the chromone-containing phenylhydrazone compound in preparation of an algistat.

Further provides the application of the chromone-containing phenylhydrazone compound in inhibiting the growth of blue algae.

Preferably, the cyanobacteria is synechocystis PCC 6803.

Preferably, in this application, chromone-containing phenylhydrazone compounds EC₅₀0.8 to 29.8 μ M.

The invention provides a chromone-containing phenylhydrazone compound with an inhibiting effect on the growth of synechocystis PCC6803 and a preparation method thereof. The molecular structure of the compound is shown as formula I, wherein R¹Selected from hydrogen, halogen, nitro, hydroxy, carboxyl, C₁-C₄An alkyl group; r²Selected from hydrogen, bromine, hydroxyl or nitro; r³Selected from hydrogen or hydroxy; r⁴Selected from hydrogen, halogen, nitro, trifluoromethyl or hydroxy; r⁵Selected from hydrogen or hydroxyl. On the basis, the invention further provides a preparation method of the compound, which comprises the step of reacting benzoyl hydrazine or a substitute thereof with 3-formyl chromone or a substitute thereof in an ethanol environment containing acetic acid to generate the compound. The compound has good growth inhibition effect on synechocystis PCC6803, and can be used for preparing related algistat products; experimental verification shows that the series of compounds inhibit EC of Synechocystis PCC6803₅₀The value is in the range of 0.8-29.8 mu M, and the high activity of the blue algae inhibitor is fully proved, so that strong support is provided for the application of the blue algae inhibitor.

Drawings

FIG. 1 is a scheme of the synthesis of compounds of the present invention.

Detailed Description

Hereinafter, specific embodiments of the present invention will be described in detail. Well-known structures or functions may not be described in detail in the following embodiments in order to avoid unnecessarily obscuring the details. Approximating language, as used herein in the following examples, may be applied to identify quantitative representations that could permissibly vary in number without resulting in a change in the basic function. Unless defined otherwise, technical and scientific terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The compound for inhibiting the growth of Synechocystis PCC6803 provided by the invention is a chromone-containing phenylhydrazone compound: the nitrogen' - [ (4-oxo-4-hydro-chromone-3-) methylene ] benzoyl hydrazine has a structural general formula shown in the specification;

in the general formula I, R¹Represents hydrogen, halogen, nitro, hydroxy, carboxy, C₁-C₄An alkyl group; r²Represents hydrogen, bromine, hydroxyl, nitro; r³Represents hydrogen or hydroxy; r⁴Represents hydrogen, halogen, nitro, trifluoromethyl, hydroxyl; r⁵Represents hydrogen or hydroxy; r¹，R²，R³，R⁴，R⁵The substituents represented are the same or different.

The compound with the general formula I has a good inhibition effect on cyanobacteria synechocystis PCC6803, and can be used as an effective component of an algicide.

The preparation method of nitrogen '- [ (4-oxo-4-hydro-chromone-3-) methylene ] phenylhydrazide represented by the general formula I is that the compound represented by the general formula II and the compound represented by the general formula III are added with a catalytic amount of acetic acid in an ethanol solvent and directly react at room temperature to obtain the nitrogen' - [ (4-oxo-4-hydro-chromone-3-) methylene ] phenylhydrazide. As shown in fig. 1.

The reaction is carried out in an ethanol solvent, a catalytic amount of acetic acid is added as a catalyst, the reaction is carried out at room temperature for 2 hours to obtain a better yield, the extraction filtration and the ethanol washing are carried out, and a filter cake is dried to obtain a product, so that the operation is simple.

The preparation of the compounds of formula I of the present invention is illustrated in more detail by example 1.