CN113292553A - Arylthiazole-tryptamine compound for killing algae by skeletonema costatum and composition agent thereof - Google Patents
Arylthiazole-tryptamine compound for killing algae by skeletonema costatum and composition agent thereof Download PDFInfo
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- CN113292553A CN113292553A CN202110515190.0A CN202110515190A CN113292553A CN 113292553 A CN113292553 A CN 113292553A CN 202110515190 A CN202110515190 A CN 202110515190A CN 113292553 A CN113292553 A CN 113292553A
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- skeletonema costatum
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- arylthiazole
- tryptamine
- algicidal
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- 241000206732 Skeletonema costatum Species 0.000 title claims abstract description 42
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- 230000002353 algacidal effect Effects 0.000 claims description 31
- -1 dimethyl tertiary amine Chemical class 0.000 claims description 19
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 19
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- DQKWXTIYGWPGOO-UHFFFAOYSA-N (2,6-dibromo-4-cyanophenyl) octanoate Chemical compound CCCCCCCC(=O)OC1=C(Br)C=C(C#N)C=C1Br DQKWXTIYGWPGOO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an arylthiazole-tryptamine compound for killing algae by skeletonema costatum and a composite agent thereof. The composition has the advantages of simple synthesis/configuration, remarkable effect, lasting drug effect, high biological safety and the like, can ensure the biological safety, and can inhibit the growth of skeletonema costatum for a long time, and the growth of skeletonema costatum still has no rebound after 10 days. Is suitable for industrial production and popularization.
Description
Technical Field
The invention relates to a skeletonema costatum algae-killing compound, and relates to a skeletonema costatum algae-killing composition containing the compound, belonging to the technical field of mariculture and marine organism resource utilization.
Background
The large-area outbreak of marine algal blooms directly influences the stability of a marine ecosystem and the healthy development of marine industries such as aquaculture industry and the like. In recent years, Skeletonema costatum is found to be a diatom red tide species which has the greatest influence on offshore areas of China, and is not only a culprit to cause multiple red tides in the estuary sea area, but also to compete for nutrition with kelp and laver in an economic seaweed culture area, so that a large amount of economic algae are discolored, rotten and even die. It has been shown that excessive proliferation of skeletonema costatum can also deeply damage gills of salmon in the Atlantic ocean, leading to death of the fish.
At present, the killing methods for skeletonema costatum can be roughly divided into three types: physical, chemical and biological methods. Wherein the physical method uses power or mechanical method to stir the marine substrate (such as sewage interception, dredging, mechanical algae removal, etc.), and relies on the self-cleaning ability of the sea to promote the recovery of the living environment of the benthic organisms. The disadvantages of this method are the high cost, difficulty in large area application and time and labor consuming. The chemical method is a method for removing algae by directly killing algae cells or flocculating and settling algae by putting various chemical reagents. Obviously, the method for killing red tide algae by adding chemicals into the water body has the most direct effect and is easy to operate, however, the used chemicals can be remained in seawater, and the residues not only can cause damage to the marine ecosystem, but also can easily enter the human body through a food chain, thereby threatening the health of human beings. Chemical agents such as prometryn, bromoxynil octanoate, simazine, ametryn, etc., which are commercially available, have been proved to enter the human body through the food chain, causing serious lesions in the secretory system, nervous system, reproductive system, etc., of the human body. The overproof chemical residue is a common problem in the aquaculture industry, and the overproof prometryn residue is found from 3 shellfish products imported from China and 14 shellfish products imported from China in total in 4-8 months in 2012. Although the biological method has the advantages of high efficiency, economy, no secondary pollution and the like, the biological method is still limited in the starting stage and the application range and is only suitable for being used in culture water areas.
Obviously, the development of the green, low-toxicity and environment-friendly algicide meets the requirements of modern marine red tide prevention and control and modern breeding industry. Recently, some bacteria, algae and plants in the sea or land can generate or release specific algae inhibiting active substances to kill algae cells specifically so as to achieve the algae inhibiting effect. For example, it has been shown that the filtered culture solution of Ulva lactuca has a significant inhibitory effect on the growth of Skeletonema costatum (CN1850631[ P ]). However, this inhibitory effect was only maintained for 2 days, and on day 3 the algae again recovered, with a slightly higher growth rate than before. In addition, vanillic acid, p-hydroxybenzoic acid and pyrogallic acid can also inhibit the growth of skeletonema costatum under higher concentration conditions (concentration is more than or equal to 128mg/L) (3 phenolic acids have the inhibition effect on the growth of skeletonema costatum [ J ]. environmental science and technology, 2015,038(003) (26-30.). Salicornia europaea is also found to be capable of remarkably inhibiting the growth of skeletonema costatum and reducing the concentration of chlorophyll in a water body for growing algae (halophyte Salicornia europaea growth inhibition [ J ] China science: life science, 2012,42(05): 419-426.). Recently, a research group uses natural algae inhibiting compounds Bacillamide A-C as a template (Tetrahedron Lett.2003,44 (43): 8005-. In the process of in-depth development, we find that: the aryl-tryptamine algae-killing active substance has better solubility only in dimethyl sulfoxide, and has the problems of partial precipitation and precipitation under the conditions of high concentration and long-term standing.
Disclosure of Invention
The invention aims to solve the technical problem of providing an arylthiazole-tryptamine compound for killing algae by skeletonema costatum and a composite agent thereof, (1) the water solubility of the product is improved by introducing methoxyl into tryptamine groups; (2) the skeletonema costatum algae-killing composition which is based on aryl thiazole-4-methoxytryptamine/isothiazolinone as a core active substance, is environment-friendly, has lasting drug effect and good water solubility is developed by means of compatibility with a cationic surfactant and other additives, improvement of product stability and the like.
The technical scheme of the invention is as follows:
the arylthiazole-tryptamine compound used as the algicidal substance of skeletonema costatum is characterized in that the characteristic structure of the compound is shown as a general formula I:
the algae-killing composition of skeletonema costatum of arylthiazole-tryptamine compounds is characterized in that arylthiazole-tryptamine and isothiazolinone of a general formula II are taken as effective active substances and are combined with biologically safe auxiliary components and solvents.
Preferably, the mass percentages of the arylthiazole-tryptamine and the isothiazolinone are (1-10): 1.
further preferably, the mass percentages of the arylthiazole-tryptamine and the isothiazolinone are 2: 1.
preferably, the concentration of the total weight of the arylthiazole-tryptamine and the isothiazolinone in the composition is 1-20 mg/L, and the balance of the composition is biologically safe auxiliary components and solvents.
Preferably, the biologically safe adjuvant component comprises a solvent component that can be used in algicides but does not chemically interact with the active substance or adversely affect the efficacy of the drug, or this nonionic surfactant component, or a zwitterionic surfactant component, or other adjuvant components including anti-freeze, anti-foam, co-solvents, stabilizers, and preservatives.
Further preferably, the nonionic surfactant is cocamidopropyl dimethyl tertiary amine, stearamidopropyl dimethylamine, cocomonoethanolamide, octadecanamidopropyl dimethyl tertiary amine, alkylphenol ethoxylates TX-10, oleamidopropyl dimethyl tertiary amine, or lauramidopropyl dimethyl tertiary amine.
More preferably, the nonionic surfactant is lauramidopropyl dimethyl tertiary amine, and the concentration of the lauramidopropyl dimethyl tertiary amine in the composition agent is 0.5-5 mg/L.
Still more preferably, the zwitterionic surfactant is dodecyl dimethyl betaine, imidazoline CAD-40, or octadecyl dimethyl betaine.
More preferably, the zwitterionic surfactant is dodecyl dimethyl betaine, and the concentration of the dodecyl dimethyl betaine in the composition is 0.5-5 mg/L.
The arylthiazole-tryptamine compound and the algicide composition have the following beneficial effects:
firstly, the arylthiazole-4-methoxytryptamine, isothiazolinone, assistant, solution composition and application thereof provided by the invention have good compatibility in a certain proportion range, show obvious addition effect, have excellent combined control effect, are obviously improved compared with single use, reduce the use amount of active ingredients and reduce the medication cost.
Secondly, the algicidal composition provided by the invention has the advantages of environmental friendliness, low toxicity, high biocompatibility and the like, and can survive 5 hours after the composition is added into experimental zebra fish.
Thirdly, the invention provides the arylthiazole-tryptamine effective component of the algicide composition and the application thereof, the synthesis process is simple, the raw materials are low in price, and the large-scale preparation and popularization are facilitated.
Fourthly, compared with the condition that the single aryl-tryptamine algicide is only dissolved in the organic solvent dimethyl sulfoxide, the composition can be dissolved in deionized water and alcohol solvent with high biosafety.
Fifth, isothiazolinone is a kind of biocide which can destroy algae DNA, the invention finds that the addition of a small amount of isothiazolinone can inhibit the growth of skeletonema costatum for a long time while ensuring the biological safety, and the growth of skeletonema costatum still has no rebound after 10 days.
And sixthly, the introduction of the nonionic surfactant and the zwitterionic surfactant can promote the long-term uniform and stable storage of the combined agent solution.
Seventh, the arylthiazole-tryptamine compound of the invention has the advantages of good algae inhibiting activity and good compatibility.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 4-ethoxybenzothiazole-5-methoxytryptamine (compound 5) prepared by the present invention.
FIG. 2 is the nuclear magnetic carbon spectrum of 4-ethoxy benzothiazole-5-methoxy tryptamine (compound 5) prepared by the present invention.
FIG. 3 is a graph comparing the algae killing data of 4-ethoxybenzothiazole-5-methoxytryptamine (compound 5) and isothiazolinone prepared according to the present invention in different ratios.
FIG. 4 is a graph comparing the effectiveness of different concentrations of the algicidal composition of the present invention.
FIG. 5 is a graph of the long-lasting inhibition of the algicidal combination formulation (13mg/L) prepared in accordance with the present invention.
FIG. 6 is a microscopic view of the live skeletonema costatum (A) and dead skeletonema costatum (B) after killing.
FIG. 7 is a comparative graph of toxicity test of zebra fish. Adding algicidal active substances for 3 hours, and keeping the zebra fish alive after 5 hours (A); the algicidal composition is added, and the zebra fish still survive after 5 hours (B); in the control group, the same concentration and volume of glyphosate was added, and zebrafish died after 30 minutes (C).
FIG. 8 is a graph comparing the solubility of arylthiazole-tryptamine algicides and the algicidal compositions of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples, experimental data and figures.
And (3) synthesizing the 4-ethoxy benzothiazole-5-methoxy tryptamine (5).
Dissolving 10mmol of 5-methoxytryptamine 4 in 50ml of dry dichloromethane, dropwise adding 12mmol of trimethylaluminum in n-hexane solution to the reaction system under ice water condition to generate bubbles, and thenThe solution gradually becomes clear, the temperature is raised to the normal temperature for reaction for 0.5 hour, 100ml of dichloromethane solution dissolved with 10mmol of 4-ethoxybenzothiazole methyl ester 3 is dripped into the reaction system, after stirring for 5 hours, 1N hydrochloric acid solution is used for quenching reaction, water and dichloromethane are added, organic phases are merged after three times of extraction, after drying, filtering and spin drying through anhydrous sodium sulfate, column chromatography separation is carried out to obtain 4-ethoxybenzothiazole-5-methoxytryptamine 5, and the yield is 87%. Spectroscopic data for compound 5:1H-NMR(CDCl3,400MHz):δ7.99(s,1H),7.98(s,br,1H),7.75(d,J＝9.2Hz 2H),7.60(t,J＝5.6Hz,1H),7.28(d,J＝9.2Hz,1H),7.07-7.09(m,2H),6.92(d,J＝9.2Hz,2H),6.86(dd,J＝2.0Hz,J＝13.2Hz,1H),4.08(q,J＝6.0Hz,2H),3.75-3.83(m,2H),3.79(s,3H),3.08(t,J＝11.2Hz,2H),1.44(t,J＝6.0Hz,3H).13C-NMR(CDCl3100MHz) delta 168.1,161.0,154.2,131.5,128.4,128.2,125.7,122.9,121.8,114.9,113.1,112.6,112.0,100.5,63.8,55.9,40.0,25.6, 14.8; high resolution mass spectrometry: c23H23N3O3Theoretical molecular weight of S444.1358, found 444.1379.
The preparation method of the 4-ethoxy benzothiazole methyl ester comprises the following steps:
adding EDCI (40mmol), dichloromethane, p-ethoxybenzoic acid 1(40mmol), triethylamine (80mmol), azido cystine dimethyl ester 2(10mmol) and triphenylphosphine (80mmol) into a round-bottom flask in sequence under stirring at room temperature, stirring for reaction for 5h at 50 ℃, adding DBU (120mmol) and bromotrichloromethane (100mmol) into the system in sequence after the reaction is finished, and stirring for reaction for 3 h. After the reaction was complete, an equal volume of saturated ammonium chloride solution was added, extraction was performed with dichloromethane (3X 150ml), the organic layer was dried over anhydrous sodium sulfate, spun dry, and washed with VPetroleum ether/VEthyl acetateColumn chromatography 2:1 gave compound 3 as a pale yellow solid in 69% yield.
The nuclear magnetic hydrogen spectrum of the 4-ethoxy benzothiazole-5-methoxy tryptamine is shown in figure 1, and the nuclear magnetic carbon spectrum of the 4-ethoxy benzothiazole-5-methoxy tryptamine is shown in figure 2. As can be seen from fig. 1 and 2: thiazole (hydrogen spectrum: δ 7.99(s, 1H); carbon spectrum δ 168.1, 154.2,125.7), methoxy (hydrogen spectrum: δ 3.79(s,3H), carbon spectrum: δ 55.9), indole (hydrogen spectrum: δ 7.28(d, J ═ 9.2Hz,1H),7.07-7.09(m,2H),6.86(dd, J ═ 2.0Hz, J ═ 13.2Hz,1H), carbon spectrum: δ 161.0,122.9,121.8,114.9,113.1,112.6,112.0,100.5).
As shown in FIG. 8(A), 13mg/L arylthiazole-tryptamine algicides precipitate after being left for 10 days (ethanol/water, 1/1); as shown in FIG. 8(B), the 19mg/L algicidal composition of the present invention remained clear after being left for 30 days (ethanol/water, 1/1).
Examples 2-4 were carried out according to the same procedure as example 1, see Table 1.
Table 1 synthetic compound data table
Second, algae killing experiment
Skeletonema costatum is provided by the first marine institute of the national marine agency, and is cultured in f/2 medium. The culture medium is prepared from aged natural seawater with pH of 7.8 and salinity of 31-33, and is sterilized with high pressure steam in automatic steam sterilizer, and added with nutrient elements. Inoculating algae cells in a logarithmic growth phase, operating in an ultra-clean workbench, culturing for 3-4 periods at the culture temperature of 20-22 ℃, illuminating by an incandescent lamp, and performing light-dark ratio for 12 hours: for 12 hours. The composition (compound 5 mass/isothiazolinone mass: 2/1) and the corresponding adjuvant were prepared as a 12mg/L solution using ethanol/purified water (v/v, 1/1), and ethanol/purified water and adjuvant at the same concentration were added to the control group. In the experiment, 0.2ml of the algicidal composition is added into 20ml of the algae solution for incubation together, the algicidal effect of the algicidal composition is evaluated by a numerical method through an Olympus BX51 microscope observation technology at different time points, and each bottle is observed and counted for 3 times in parallel.
TABLE 2 algal killing effect of compound 5 and isothiazolinone in different ratio
As shown in table 2, when compound 5 was used in combination with isothiazolinone (1:1, 2:1, 4:1), the algicidal effect was significantly improved as compared to the effect of compound 5 alone, especially, the ratio of the two was 2:1, and the algicidal effect was doubled as compared to compound 5 alone after incubation for 24 hours with added algal solution.
0.2ml of 13mg/L algicidal composition (compound 5/isothiazolinone/lauramidopropyldimethyl tertiary amine/dodecyl dimethyl betaine ═ 16/8/1/1) was added to 20ml of skeletonema costatum solution, and after incubating for 5 minutes to 5 hours, the algicidal composition had significant inhibition of skeletonema costatum. When the concentration of the algicidal composition agent is continuously increased to 19mg/L, the algicidal effect is improved by 10 times, see Table 3. These results demonstrate that the algicidal composition prepared by the present invention has an excellent killing effect on skeletonema costatum.
TABLE 3 data table of the algicidal effect of different concentrations of the combination
Third, long-acting algae killing and inhibiting experiment
The developed algicidal composition has excellent long-acting inhibition effect on skeletonema costatum, as shown in table 4, 0.2ml of 13mg/L composition has obvious long-acting inhibition effect on 20ml of skeletonema costatum in logarithmic phase, after the algicidal agent is added, the proliferation trend of skeletonema costatum is immediately inhibited, and observation lasts for ten days shows that compared with a control group, the algae density controlled by the medicine is always maintained at a lower level, and the effects of long-acting algae killing and inhibiting are achieved.
TABLE 4 Long-acting algae inhibiting and killing data sheet of algae killing composition
As can be seen from fig. 3: the compound 5 and isothiazolinone mixed agent in the ratio of 2:1 can kill skeletonema costatum within 5 minutes to one third of the original concentration, and the inhibition rate is obviously improved compared with the single compound 5.
Is a comparison graph of algae killing data of different proportions of 4-ethoxy benzothiazole-5-methoxy tryptamine (compound 5) and isothiazolinone prepared by the invention.
As can be seen from fig. 4: along with the increase of the dosage of the composition, the algae killing effect is also obviously improved, and the skeletonema costatum is almost completely killed after 5 hours at the high concentration of 19 mg/L.
As can be seen from fig. 5: the composition has excellent long-acting inhibitory effect on skeletonema costatum.
Graph of algal death under microscopic field, as in fig. 6.
Fourth, toxicity test
The algicidal composition developed by the invention has good environmental friendliness and safety. Toxicity test 0.4 ml of 13mg/L active substance 5, 0.4 ml of 13mg/L algicidal composition and 5mg/L glyphosate were added to 40 ml of aqueous solution fed with zebrafish, respectively, and the zebrafish activity and survival were observed. Experiments show that after 5 hours of co-culture, zebrafish survived and were not abnormal in the beaker with the active substance 3 and the algicidal composition, while the zebrafish died within 30 minutes after the glyphosate was added to the control group, as shown in fig. 7.
Claims (10)
1. The arylthiazole-tryptamine compound used as the algicidal substance of skeletonema costatum is characterized in that the characteristic structure of the compound is shown as a general formula I:
2. the algae-killing composition of skeletonema costatum of arylthiazole-tryptamine compounds is characterized in that arylthiazole-tryptamine and isothiazolinone of a general formula II are taken as effective active substances and are combined with biologically safe auxiliary components and solvents.
3. The skeletonema costatum algicidal composition according to claim 2, wherein the mass percentages of the arylthiazole-tryptamine and the isothiazolinone are (1-10): 1.
4. the skeletonema costatum algae-killing composition according to claim 3, wherein the mass percentage of the arylthiazole-tryptamine and the isothiazolinone is 2: 1.
5. the skeletonema costatum algicidal composition according to claim 2, 3 or 4, wherein the total concentration of the arylthiazole-tryptamine and the isothiazolinone by weight in the composition is 1-20 mg/L, and the balance is biologically safe auxiliary components and solvents.
6. The skeletonema costatum algicidal composition according to claim 2, 3 or 4 wherein the biosafety adjunct ingredients include solvent ingredients that can be used in algicidal agents without chemically interacting with the active substance or adversely affecting the efficacy of the drug, or the nonionic surfactant ingredients, or the zwitterionic surfactant ingredients, or other adjunct ingredients including anti-freeze agents, anti-foam agents, co-solvents, stabilizers and preservatives.
7. The skeletonema costatum algicidal composition of claim 6 wherein the nonionic surfactant is cocamidopropyl dimethyl tertiary amine, stearamidopropyl dimethylamine, cocoyl monoethanolamide, caprylocamidopropyl dimethyl tertiary amine, alkylphenol ethoxylate TX-10, oleamidopropyl dimethyl tertiary amine or lauramidopropyl dimethyl tertiary amine.
8. The skeletonema costatum algae-killing composition according to claim 7, wherein the nonionic surfactant is lauramidopropyl dimethyl tertiary amine, and the concentration of the lauramidopropyl dimethyl tertiary amine in the composition is 0.5-5 mg/L.
9. The skeletonema costatum algicidal composition of claim 6 wherein the zwitterionic surfactant is dodecyl dimethyl betaine, imidazoline CAD-40 or octadecyl dimethyl betaine.
10. The skeletonema costatum algae-killing composition as claimed in claim 9, wherein the zwitterionic surfactant is dodecyl dimethyl betaine, and the concentration of the dodecyl dimethyl betaine in the composition is 0.5-5 mg/L.
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| CN115160207A (en) * | 2022-04-21 | 2022-10-11 | 烟台大学 | Benzoyl thiourea compound, preparation method thereof and application of red tide algae algicide |
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| CN115160207A (en) * | 2022-04-21 | 2022-10-11 | 烟台大学 | Benzoyl thiourea compound, preparation method thereof and application of red tide algae algicide |
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