CN111303068A - Structure and biological activity of a benzisothiazolinone-heterocyclic antifouling coating - Google Patents

Abstract

The invention discloses a structure and algae and barnacle larva inhibiting activity of (benzisothiazolin-3-one) -N-heterocyclic substituted compound antifouling paint and application in an algae inhibiting antifouling agent. Can be used for inhibiting marine algae and marine fouling organisms. The compound has good inhibitory activity on dinoflagellates such as chrysophyceae, Platymonas subcordiformis, navicula and other marine algae, also has good inhibitory activity on common marine fouling organisms such as barnacle larvae and the like, and can be developed into a novel marine algae inhibitor, a marine fouling organism inhibitor and the like.

Description

Structure and biological activity of a benzisothiazolinone-heterocyclic antifouling coating

technical field

The present invention relates to the structures and biological activities of benzisothiazolin-3-one-N-heterocyclic substituted compounds, and their biological activities in algae inhibition and antifouling as components of marine antifouling paints. The compounds can be used for growth inhibition of marine algae, inhibition of marine fouling biological barnacle larvae and the like. Applicable marine algae include, but are not limited to: Isochrysis globosa, Flat algae subcordiformis, Navicula, etc.; common marine fouling organisms include but are not limited to: barnacles, mussels, lime worms, etc.

Background technique

Benzisothiazolin-3-one (BIT) and its derivatives have attracted great attention due to their wide range of activities such as algal inhibition and inhibition of marine fouling organism larvae, and are widely used in industry, agriculture, marine, food, etc. and medicine fields. Heterocyclic compounds containing N and S have unique insecticidal, bacteriostatic and other good bioinhibitory activities, and are often used as the main components or structural components of medicines and pesticides. Heterocyclic compounds such as pyridine, triazole and thiazole are widely used in pesticides, herbicides and fungicides in agriculture. The invention utilizes the principle of active subgroup splicing, integrates biologically active structural units such as BIT and heterocyclic structures into a molecular structure, and obtains a novel sterilization and antifouling structure of heterocyclic substituted benzisothiazolin-3-ones Compounds were tested for their inhibitory effects on marine algae and barnacles as active ingredients in antifouling coatings.

SUMMARY OF THE INVENTION

The purpose of the present invention is to explore a compound with good activity and broad-spectrum inhibition of marine algae and marine fouling organisms, and to provide the structure of a new type of benzisothiazole derivative with algae inhibition and marine fouling organism inhibition. The general structural formula of a class of benzisothiazole derivatives proposed by the present invention is shown in FIG. 1 .

figure 1

Wherein, R ₁ is selected from H, CH ₃ , OCH ₃ , F, Cl, Br, NO ₂ , SCH ₃ , CN, COCH ₃ , CONH ₂ and the like. R ₂ is selected from: pyridyl, methylpyridyl, triazolyl, thiazolyl, benzothiazolyl.

The structures of this class of compounds will be illustrated by specific examples below.

Example 1

Algal growth inhibitory activity assay. The algal liquid was cultured in an artificial climate box. The culture conditions of Isochrysis globosa were salinity of 5%-10%, temperature of 25±1℃, pH of 8.0±0.5, and light intensity of 7000-9000 lux; The culture conditions of Phyllostachys are 8%-15%, the temperature is 25±1℃, the pH is 8.0±0.5, and the light intensity is 5000-10000 lux; the culture conditions of Navicula are 10%-15%, the temperature is 25±0.5 1°C, pH 8.0±0.5, light intensity 3000-5000 lux.

The maximum absorption wavelengths of Isochrysis globosa, Planophyte subcordiformis and Navicula algae were measured by UV-Vis spectrophotometer at 428 nm, 680 nm and 342 nm, respectively. After the algae liquid was cultivated in an artificial incubator to the exponential growth phase, it was diluted with the culture medium to different concentrations, and the concentration of each dilution was measured by a hemocytometer, and the average value was measured 3 times. Measure the absorbance value of algae liquid at the maximum ultraviolet absorption wavelength of each algae liquid with a UV-Vis spectrophotometer, and make a standard curve with the absorbance value as the abscissa and the concentration as the ordinate.

According to the absorbance value-concentration standard curve of algal liquid, select 50 mL of algal liquid with absorbance value between 0.05-0.1 and place it in a 100 mL conical flask. Take 1 mL of the test compound with a concentration of 0.2 mg/mL and add it to the conical flask, set three parallel samples in each group, select the same concentration of BIT and blank as the control group, and measure the absorbance value of each conical flask every 12 hours. According to the algal liquid absorbance value-algal liquid concentration curve equation, the corresponding algal liquid concentration was obtained, and the time-algal liquid concentration curve was drawn.

Taking the compounds shown in Fig. 2 as an example, the growth-inhibitory activities of the compounds shown in Fig. 2 were measured against Isochrysis globosum, Flat algae subcordiformis, and Navicula algae, as shown in Fig. 3-5.

Accurately weigh 10 mg of the test compound, dissolve it in 10 mL of dimethyl sulfoxide, and dilute the target compound with fresh seawater after filter sterilization to prepare the test compound with a mass concentration of 2, 4, 6, 8, and 10 mg/L. Solution, and set BIT as the control group, each group set up 3 parallel experiments, repeated 3 times. Observing with the naked eye, the swimming barnacle larvae were selected and placed in a petri dish, and the number of barnacle larvae in each petri dish was 30 (the barnacle larvae should be rinsed with the same concentration of the test solution before entering). The survival of barnacle larvae was observed after 12h and 24h with a stereo microscope, and the number of dead barnacle larvae was recorded. To ensure the accuracy of the experiment, the dead larvae were extracted in time. During observation, barnacle larvae can be considered dead if they sink to the bottom of the petri dish and stop swimming for more than 15 seconds. The toxic effects of the compounds on barnacle larvae are shown in Table 1 and Table 2.

Table 2 Toxic effects of compounds on barnacle larvae (24h)

It can be seen from Table 2 that when the concentration of the tested compounds was 2.0 mg/L at 24 h, the lethality to barnacle larvae reached more than 96%, and compounds 3a and 3e were completely lethal to barnacle larvae. It can be seen that each compound has strong poisoning effect on barnacle larvae, and the poisoning effect is better than that of BIT. At the same time, it can be seen that the mortality of barnacle larvae is also increasing with the continuous increase of the tested concentration. In the range of compound mass concentration of 0.1 mg/L-1.0 mg/L, the death trend of barnacle larvae is the largest.

At the same experimental concentration, the lethality of barnacle larvae at 12 h was less than that at 24 h, which indicated that the toxic effects of each compound on barnacles increased with time. At the same time, it can be seen that at 12 h and 24 h, at low concentrations, the change trend of the lethality of each compound to barnacle larvae is much greater than that of BIT, which indicates that trace compounds have obvious poisoning effect on barnacle larvae.

The above description is only a detailed description of the embodiment of the present invention, but the present invention is not limited to the above-mentioned embodiment. Various embodiments may be realized with modifications within the scope of the claims and description, and such modifications are intended to belong to the scope of the present invention.

Claims (8)

1. a (benzisothiazolin-3-ketone)-N-heterocyclic substituted aminoacetamide compound, its structure is shown in formula (I):

I Wherein, R ₁ is selected from: H, CH ₃ , OCH ₃ , F, Cl, Br, NO ₂ , SCH ₃ , CN, COCH ₃ , CONH ₂ and the like. 2. R ₂ is selected from the group consisting of: pyridyl, methylpyridyl, triazolyl, thiazolyl, benzothiazolyl. 3. the structure of the compound represented by formula I according to claim 1, is characterized in that, is mainly made up of compound II and III:

II III Wherein, R ₁ is selected from: H, CH ₃ , OCH ₃ , F, Cl, Br, NO ₂ , SCH ₃ , CN, COCH ₃ , CONH ₂ and the like. 4. R ₂ is selected from the group consisting of: pyridyl, methylpyridyl, triazolyl, thiazolyl, benzothiazolyl. 5. The structure of the compound represented by formula I according to claim 2, characterized in that: containing benzo[ d ]isothiazolin-3(2H)-one, pyridyl, methylpyridyl, triazolyl, Thiazolyl, benzothiazolyl and other structures. 6. The use of the compound represented by formula 1 according to claim 1 in the preparation of an antifouling agent, mainly for the inhibition of common marine algae, the inhibition of common marine fouling biological barnacle larvae, and the like. 7. Applicable marine algae include but are not limited to: Isochrysis globosa, Planophyte subcordiformis, Navicula, etc.; common marine fouling organisms include but are not limited to: barnacle larvae, etc. 8. The form of the compound represented by formula I according to claim 1, including raw materials and preparations thereof, etc.

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